WO2007138906A1 - Organic electroluminescent device and full color light-emitting device - Google Patents

Abstract

Disclosed is an organic electroluminescent device (10) comprising an anode (1), a first light-emitting layer (3), a charge blocking layer (4), a second light-emitting layer (5) and a cathode (7) sequentially arranged in this order. The first light-emitting layer (3) and the second light-emitting layer (5) respectively contain a host material and a dopant, and the energy gap of the host material of the first light-emitting layer (3) is smaller than the energy gap of the host material of the second light-emitting layer (5). The host material of the first light-emitting layer (3) is a hole transporting material, while the host material of thesecond light-emitting layer (5) is an electron transporting material. The affinity level of the charge blocking layer (4) is lower than the affinity level of the host material of the second light-emitting layer (5) by 0.2 eV or more, and the ionization potential (Ie1) of the charge blocking layer (4) and the ionization potential (Ih1) of the host material of the first light-emitting layer (3) satisfy the following relation (1). Ie1 < Ih1 + 0.1 (eV) (1)

Description

 Specification

 Organic electoluminescence device and full-color light emitting device

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to an organic electoluminescence device and a full-color light emitting device using the same.

 Background art

 [0002] In recent years, the development of white organic electroluminescence devices (organic EL devices) can be used for mono-color display devices, lighting applications such as knocklights, and full-color display devices using color filters. It is being actively conducted. In particular, when a white organic EL element is used for illumination, a white organic EL element having a high luminous efficiency that is equal to or higher than the luminous efficiency of a fluorescent lamp, for example, is required.

 [0003] Many methods for obtaining white light emission by an organic EL element have been disclosed. In these methods, there are few that obtain a white color with only one kind of light emitting material, and usually two or three kinds of light emitting materials are made to emit light simultaneously in one organic EL device. When using two types of luminescent materials, select a blue-based and yellow-red luminescent material that is complementary to it, but a yellowish-red-based luminescent material often increases in reddish white. It tends to be.

 [0004] To solve this problem, in Patent Document 1, in the type in which the light emitting layer is divided into two, the light emitting color becomes red by making the light emitting layer on the anode side where the light emitting region of the light emitting layer is easily biased into a blue light emitting layer We have found that the tendency to be biased can be counteracted, and have proposed a white element that suppresses color changes. However, the luminous efficiency was not always at a sufficient level.

 [0005] Patent Document 2 discloses an organic EL element in which a light emitting layer is laminated in the order of a red light emitting layer, a blue light emitting layer, and a green light emitting layer from the anode side. Furthermore, a technique for suppressing a color change accompanying an increase in driving current by doping a red light emitting layer used in the red light emitting layer into the blue light emitting layer is also disclosed. However, the luminous efficiency was not always sufficient.

[0006] On the other hand, as a technique for emitting white light in a well-balanced manner, several techniques for providing a charge barrier layer between a plurality of light emitting layers have been disclosed. For example, Patent Document 3 discloses an organic EL device that emits white light by laminating an anode, a hole transporting blue light emitting layer, an electron transporting carrier recombination region control layer, an electron transporting red light emitting layer, and a cathode in this order. Yes. However, the driving voltage was high because the affinity level of the carrier recombination region control layer was larger than the affinity level of the hole transporting blue light emitting layer. Also, electrons are less likely to be injected into the hole-transporting blue light-emitting layer with the driving time, the light emission intensity of the hole-transporting blue light-emitting layer is reduced, and the emission color tends to be biased toward the red light emission of the electron-transporting light-emitting layer. It was.

[0007] Patent Document 4 discloses a white light-emitting organic EL device in which two electron-transporting light-emitting layers are arranged via a charge barrier layer. However, the holes injected from the anode are mostly consumed in the first light-emitting layer, and pass through the charge barrier layer and are supplied to the second electron-transporting light-emitting layer. Due to the small amount, the efficiency of white light emission is low.

 [0008] In Patent Document 5, an anode, a first light emitting layer, a charge barrier layer, a second light emitting layer, and a cathode are stacked in this order, and the ion barrier potential of the charge barrier layer is set to the ion barrier of the first light emitting layer. A white light emitting organic EL device is disclosed in which the potential level of the charge barrier layer is set to 0. leV or more higher than the potential, and the affinity level of the second light emitting layer is set to 0. leV or less. However, since the charge barrier layer has both functions of an electron barrier and a hole barrier, there is a problem that the drive voltage becomes high.

In addition, white elements are disclosed in Patent Document 6 and Patent Document 7, but neither of them has sufficient light emission efficiency.

 Patent Document 1: Japanese Patent Laid-Open No. 2003-272857

 Patent Document 2: JP-A-2004-235168

 Patent Document 3: JP-A-8-78163

 Patent Document 4: International Publication No. 2005Z099313 Pamphlet

 Patent Document 5: International Publication No. 2005Z112518 Pamphlet

 Patent Document 6: Japanese Unexamined Patent Application Publication No. 2005-100921

 Patent Document 7: US Publication No. 2006Z0088729

[0010] In view of the above problems, the present invention has color rendering properties suitable for display and lighting applications, and emits light. The object is to provide an organic EL device with high efficiency and little change in chromaticity!

 Disclosure of the invention

 [0011] In order to solve this problem, as a result of intensive studies by the present inventors, it was found that the following elements have high color rendering properties and luminous efficiency, and little change in chromaticity, thereby completing the present invention. It was.

 [0012] According to the present invention, the following organic EL element and full-color light-emitting device are provided.

 1. An anode, a first light emitting layer, a charge barrier layer, a second light emitting layer, and a cathode are laminated in this order, and the first light emitting layer and the second light emitting layer each contain a host material and a dopant, and 1 The energy gap force of the host material of the light emitting layer is smaller than the energy gap of the host material of the second light emitting layer,

 The host material of the first light emitting layer is a hole transporting material, the host material of the second light emitting layer is an electron transporting material,

 The affinity level force of the charge barrier layer is 0.2 eV or more smaller than the affinity level of the host material of the second light emitting layer,

 Ion potential (Iel) of the charge barrier layer and ion potential (Ihl) 1S of the host material of the first light emitting layer 1S An organic electoluminescence device that satisfies the following relationship (1).

 IeKIhl + O. 1 (eV) · · · (1)

 2. It includes an anode, a first light emitting layer, a charge barrier layer, a second light emitting layer, a third light emitting layer, and a cathode stacked in this order,

 The first light-emitting layer, the second light-emitting layer, and the third light-emitting layer contain a host material and a dopant, respectively;

 The energy gap force of the host material of the first light emitting layer is smaller than the energy gap of the host material of the second light emitting layer,

 The host material of the first light emitting layer is a hole transporting material;

 The host material of the second light emitting layer and the third light emitting layer is an electron transporting material, and the charge barrier layer is a hole transporting material,

The ion barrier potential (Iel) of the charge barrier layer and the host material of the first light emitting layer On-potential (Ihl) force An organic electroluminescent device that satisfies the following relationship (1).

 IeKIhl + O. 1 (eV) · · · (1)

 3. The organic electroluminescence device according to 2, wherein the affinity level force of the charge barrier layer is 0.2 eV or more smaller than the affinity level of the host material of the second light emitting layer.

4. The energy gap force of the host material of the first light-emitting layer 4. The organic electroreductive element according to any one of 1 to 3, which is 0.4 eV or more smaller than the energy gap of the host material of the second light-emitting layer.

 5. The organic electroluminescent device according to 1, wherein the dopant of the first light emitting layer is a red dopant, and the dopant of the second light emitting layer is a blue dopant.

 6. The organic electroluminescence according to 2 or 3, wherein the dopant of the first light emitting layer is a red dopant, the dopant of the second light emitting layer is a blue dopant, and the dopant of the third light emitting layer is a green dopant. element.

 7. The organic electroluminescence device according to any one of 1 to 6, wherein the charge barrier layer contains a light emitting material.

 8. The organic electroluminescent device according to 7, wherein the light-emitting material of the charge barrier layer is a green dopant.

 9. The organic electoluminescence device according to any one of 1 to 8, which has a hole transport layer adjacent to the first light emitting layer between the anode and the first light emitting layer.

 10. The organic electroluminescent device according to 9, wherein the material forming the hole transport layer and the material forming the charge barrier layer are the same material.

 11. The first light-emitting layer or the first organic layer, which is an organic layer close to the anode, has a force containing an oxidizing agent, and the second light-emitting layer or the second organic layer, which is an organic layer close to Z or the cathode The organic electoluminescence device according to any one of 1 to 10, which contains a reducing agent.

 12. The host material of the first light emitting layer is a compound represented by the following formula (1), and the dopant of the first light emitting layer is a compound having a fluoranthene skeleton or a perylene skeleton 1 to: L 1 The organic electoluminescence device according to any one of the above.

X— (Y) n (1) (In the formula, X is a condensed aromatic ring group having 3 or more carbon rings,

 Y is a group selected from a substituted or unsubstituted aryl group, a substituted or unsubstituted dialyl amino group, a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group,

 n is an integer of 1 to 6, and when n is 2 or more, Y may be the same or different. )

13. The organic electroluminescent device according to 12, wherein the compound having a fluoranthene skeleton or a perylene skeleton is an indenoperylene derivative represented by the following formula (2) or formula (3).

[Chemical 1]

Ar²及び Ar³は、それぞれ置換もしくは無置換の芳香環基又は置換もし くは無置換の芳香族複素環基であり、 〜 ⁸は、それぞれ水素、ハロゲン、アルキ ル基、アルコキシ基、アルキルチオ基、ァルケ-ル基、ァルケ-ルォキシ基、ァルケ 二ルチオ基、芳香環含有アルキル基、芳香環含有アルキルォキシ基、芳香環含有ァ ルキルチオ基、芳香環基、芳香族複素環基、芳香環ォキシ基、芳香環チォ基、芳香 環アルケニル基、アルケニル芳香環基、アミノ基、カルバゾリル基、シァノ基、水酸基 、 -COOR¹ (R¹'は水素、アルキル基、ァルケ-ル基、芳香環含有アルキル基又は 芳香環基である。）、 COR²' (R²'は水素、アルキル基、アルケニル基、芳香環含有 アルキル基、芳香環基又はアミノ基である）、又は OCOR³' (R°はアルキル基、ァ ルケニル基、芳香環含有アルキル基又は芳香環基である）である。 〜 ¹⁸の隣接 する基は、互いに結合して、又は置換している炭素原子と共に環を形成していてもよ い。） (Where

Ar ² and Ar ³ are each a substituted or unsubstituted aromatic ring group or a substituted if Ku unsubstituted aromatic heterocyclic group, ^1-8 each represent hydrogen, halogen, alkyl group, alkoxy group, alkylthio group , Alkenyl group, alkoxy group, alkenyl group, aromatic ring-containing alkyl group, aromatic ring-containing alkyloxy group, aromatic ring-containing alkylthio group, aromatic ring group, aromatic heterocyclic group, aromatic ring oxy group, Aromatic ring thio group, aromatic ring alkenyl group, alkenyl aromatic ring group, amino group, carbazolyl group, cyano group, hydroxyl group, -COOR ¹ (R ¹ 'is hydrogen, alkyl group, alkenyl group, aromatic ring-containing alkyl group or Is an aromatic ring group), COR ² ′ (R ² ′ is hydrogen, an alkyl group, an alkenyl group, an aromatic ring-containing alkyl group, an aromatic ring group or an amino group), or OCOR ³ ′ (R ° is an alkyl group) , Alkenyl group, A scent ring is containing alkyl group or aromatic ring group). Adjacent groups of to ^18, but it may also form a ring together with the carbon atom bonded to, or substituted for each other. )

14. The organic electroluminescent device according to 13, wherein the indenoperylene derivative is a dibenzotetrafluoro-perifuranthene derivative. 15. The organic electoluminescence according to any one of 12 to 14, wherein the host material of the first light emitting layer has 4 or more condensed rings and the host material of the second light emitting layer has 3 or less condensed rings. element.

 16. The compound power represented by the formula (1) The organic electoluminescence device according to any one of 12 to 15, which is a naphthacene derivative represented by the following formula (4).

 [Chemical 2]

 ( Four )

(In formula (4), (^ to ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 nuclear carbon atoms, amino Group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 20 nuclear carbon atoms, substituted or unsubstituted 6-20 aralkylthio group, substituted or unsubstituted alkenyl group having 2-20 carbon atoms, substituted or unsubstituted aralkyl group having 7-20 carbon atoms, or substituted or unsubstituted nuclear atoms 5-20 And these may be the same or different.)

17. The organic electroluminescent device according to 16, wherein at least one of QQ ² , Q ³ and Q ^{4 in} the naphthacene derivative represented by the formula (4) is an aryl group.

 18. The organic electroreductive element according to 17, wherein the naphthacene derivative represented by the formula (4) is represented by the following formula (5).

[Chemical 3]

(In the formula (5), Q ^{3 to} Q ¹² , Q ¹⁰¹ to Q ¹⁰⁵ , Q ^{201 to} Q ² ° ⁵ each independently represents the same group as Q ^{3 to} Q ¹² in the general formula (1), These two, which may be the same or different, may be bonded to each other to form a ring.

19.In the naphthacene derivative represented by the above formula (5), at least one of Q ^{1 (n} , Q ¹⁰⁵ , Q ²⁰¹ and Q ² ° ⁵ is an alkyl group, aryl group, amino group, alkoxy group, aryloxy group, 19. The organic electoluminescence device according to 18, which is an alkylthio group, an arylthio group, an alkyl group, an aralkyl group or a heterocyclic group, which may be the same or different.

20. The organic electoluminescence device according to any one of 12 to 19, wherein the charge barrier layer comprises a tertiary amine compound, a force rubazole derivative, a compound containing a nitrogen-containing heterocyclic ring or a metal complex.

 21. A full-color light emitting device comprising a white-light-emitting organic electroluminescent device according to any one of 1 to 20 and a color filter.

 According to the present invention, it is possible to provide an organic EL device having color rendering properties, high luminous efficiency and little change in chromaticity!

 Brief Description of Drawings

FIG. 1 is a diagram showing a configuration of an organic EL element according to Embodiment 1 of the present invention. 2 is a diagram showing energy levels of a first light emitting layer, a charge barrier layer, and a second light emitting layer of the organic EL element shown in FIG. 1.

 FIG. 3 is a diagram showing a configuration of an organic EL element according to Embodiment 2 of the present invention.

 FIG. 4 is a diagram showing a configuration of an organic EL element according to Embodiment 3 of the present invention.

 FIG. 5 is a diagram showing energy levels of the first light-emitting layer, the first charge barrier layer, and the second light-emitting layer created in Example 1.

 FIG. 6 is a diagram showing energy levels of the first light-emitting layer, the first charge barrier layer, and the second light-emitting layer prepared in Comparative Example 4.

 FIG. 7 is a diagram showing the energy levels of the first light-emitting layer, the first charge barrier layer, and the second light-emitting layer prepared in Comparative Example 5.

 FIG. 8 is a diagram showing the value of CIE1931 chromaticity X with respect to the luminance of the organic EL devices fabricated in Comparative Example 1 and Examples 1 to 4.

 FIG. 9 is a diagram showing the value of CIE1931 chromaticity y with respect to the luminance of the organic EL devices fabricated in Comparative Example 1 and Examples 1 to 4.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0015] Embodiment 1

 The organic EL device according to Embodiment 1 of the present invention includes an anode, a first light emitting layer, a charge barrier layer, a second light emitting layer, and a cathode laminated in this order. Each of the first light emitting layer and the second light emitting layer contains a host material and a dopant.

 Here, the first light emitting layer includes a hole transporting material as a host material, and the second light emitting layer includes an electron transporting material as a host material. Furthermore, the energy gap of the host material of the first luminescent layer is smaller than the energy gap of the host material of the second luminescent layer! /.

 Also, the affinity level force of the charge barrier layer The ion barrier potential (Iel) of the charge barrier layer, which is 0.2 eV or more smaller than the affinity level of the host material of the second light emitting layer, and the host material of the first light emitting layer. Ion potential (Ihl) force The following relationship (1) is satisfied.

 IeKIhl + O. 1 (eV) · · · (1)

[0016] Preferably, the affinity level (Afel) of the charge barrier layer is 0.2 eV or more smaller than the affinity level (Afh2) of the host material of the second light emitting layer, which is greater than leV! Meet ) o

 KAfel≤Afh2-0. 2 (eV)

[0017] Preferably, the ion barrier potential (Iel) of the charge barrier layer and the ionization potential (Ihl) force of the host material of the first light emitting layer satisfy the following equation.

 2.5 <Iel <Ihl + 0.1 (eV)

[0018] Preferably, the energy gap (Eghl) of the host material of the first light-emitting layer is larger than 1.5 eV and smaller than the energy gap (Egh2) of the host material of the second light-emitting layer by 0.4 eV or more ( Fulfill).

 1. 5 <Eghl≤Egh2-0. 4 (eV)

FIG. 1 is a diagram illustrating an example of the configuration of the organic EL element according to the first embodiment.

 The organic EL element 10 shown in FIG. 1 has a structure in which an anode hole transport layer 2, a first light emitting layer 3, a charge barrier layer 4, a second light emitting layer 5, an electron transport layer 6 and a cathode 7 are laminated. .

 The first light emitting layer 3 and the second light emitting layer 5 contain a host material and a dopant, respectively.

 In this element 10, for example, white light emission can be obtained by making the first light emitting layer 3 emit red light and the second light emitting layer 5 emit blue light. The reason why the second light-emitting layer 5 is doped with a blue dopant is to make blue, which is generally weak in light emission, shine well and to balance white.

[0020] In the organic EL element 10, the host material of the first light emitting layer 3 close to the anode 1 side is a hole transporting material, and the host material of the second light emitting layer 5 close to the cathode 7 is an electron transporting material. is there. A charge barrier layer 4 is provided between the first light emitting layer 3 and the second light emitting layer 5. By doing so, the electron injection into the first light-emitting layer 3 and the hole injection into the second light-emitting layer 5 are performed in a well-balanced manner, and the electron blocking by the charge barrier layer 4 causes the charge barrier layer 4 and the second light-emitting layer 3 to be injected. The recombination region concentrates around the interface with the light emitting layer. Then, since the second light emitting layer 5 is doped with a blue dopant, blue light emission can be obtained efficiently. Blue light emission is generally weak, but strong blue light emission can be obtained. In the first light-emitting layer 3, the energy of blue light emitted from the second light-emitting layer 5 is also transferred to the red light of the first light-emitting layer 3 along with recombination of electrons injected through the charge barrier layer and holes from the anode side. The red light emission is also obtained by moving. Therefore, high efficiency and excellent color balance White luminescence is obtained.

Here, “hole transportability” in the present invention means that the hole mobility of the layer is larger than the electron mobility in the electric field range of 10 ² to 10 ⁸ V / cm. Preferably, the hole mobility of the first light emitting layer is 10 ⁻⁵ cm ² ZV · sec or more.

“Electron transportability” means that the electron mobility of the layer is higher than the hole mobility in the electric field range of 10 ² to 10 ⁸ V / cm. Preferably, the electron mobility of the second light emitting layer is 10 ^-6 cm ² ZV · sec or more.

 Hole or electron mobility is measured by the Time of flight method.

[0022] Note that, when the host materials of the first light emitting layer and the second light emitting layer are both electron transporting materials, the recombination region is biased toward the first light emitting layer as in Patent Document 4 of the prior art, It is difficult to obtain good white light emission.

 In addition, when the host materials of the first light emitting layer and the second light emitting layer are both hole transporting materials, the recombination region is biased to the second light emitting layer, and good white light emission is obtained. Hateful. In addition, the recombination region tends to be biased to the cathode side in the second light emitting layer. For this reason, the light emission efficiency is lowered by the quenching action of the metal cathode.

 When the host material of the first light emitting layer is an electron transporting material and the host material of the second light emitting layer is a hole transporting material, electrons are injected into the first light emitting layer and holes are injected into the second light emitting layer. Both injections are performed, resulting in a significant increase in drive voltage.

 Also, consider the case where the anode, hole-transporting blue light-emitting layer, electron-transporting carrier recombination region control layer, electron-transporting red light-emitting layer, and cathode are stacked in this order as described in Patent Document 3.

 In this case, the energy gap of blue is large! Therefore, the affinity level of the hole transporting blue light emitting layer is lowered. In addition, the electron transport carrier recombination region control layer has a generally high level of affinity. Therefore, the electron injection barrier from the electron transporting carrier recombination region control layer to the hole transporting blue light emitting layer is increased, and the driving voltage of the device is increased as a whole.

In this respect, in the configuration of the present embodiment, the blue light-emitting layer is disposed on the cathode side of the charge barrier layer, so that the gap in the power level does not become too large and high voltage is prevented. Can do.

 In the organic EL element 10, the power level of the charge barrier layer 4 is 0.2 eV or more smaller than the power level of the host material of the second light emitting layer 5. In addition, the ionic potential (Iel) of the charge barrier layer 4 and the ionic potential (Ihl) force of the host material of the first light emitting layer 3 satisfy the following relationship (1).

 IeKIhl + O. l (eV) · · · (1)

 This relationship will be described with a diagram showing energy levels.

 FIG. 2 shows the energy levels of the host material of the first light emitting layer 3, the charge barrier layer 4 and the second light emitting layer 5 of the organic EL element 10. In this figure, the upper side shows the affinity level of each layer, and the lower side shows the ionization potential. In the energy level diagram, the lower part shows a larger value. In each layer, the difference between the ion potential and the affinity level corresponds to the energy gap.

 In the organic EL element 10, the power level of the charge barrier layer 4 is 0.2 eV or more smaller than the power level of the second light emitting layer 5. That is, in FIG. 2, the charge level of the charge barrier layer 4 is positioned 0.2 eV or more higher than that of the second light emitting layer 5 (in FIG. 2, ΔΑί is 0.2 eV or more).

 The charge barrier layer 4 is a layer that restricts the injection of electrons from the second light-emitting layer 5 closer to the cathode 7 to the first light-emitting layer 3 closer to the anode 1. It is provided to control the recombination amount of the hole pair and adjust the light emission amount from each light emitting layer. Considering this function, it is necessary to have a power level that is 0.2 eV or more smaller than that of the host material of the second light emitting layer. Preferably it has a small power level of 0.5 eV or more.

 The relationship between the host material affinity level of the first light-emitting layer 3 and the charge barrier layer 4 affinity level is not particularly limited, but from the viewpoint of driving voltage, the affinity level force of the charge barrier layer 4 is not limited. It is preferable to be smaller than S〇eV.

In the organic EL element 10, the ionization potential (Iel) of the charge barrier layer 4 and the ion potential (Ihl) of the host material of the first light emitting layer 3 satisfy the above (1). This is because the increase of the drive voltage becomes a problem when the charge barrier layer 4 becomes a barrier against holes, thus preventing it. It is to do.

 The relationship between the ionic potential (Iel) of the charge barrier layer 4 and the ionic potential (Ihl) of the host material of the first light emitting layer 3 preferably satisfies the following formula (1 ′).

 IeKIhl -O. 2 (eV) · · · · (1 ')

In the organic EL element 10, the energy gap force of the host material of the first light emitting layer 3 is smaller than the energy gap of the host material of the second light emitting layer 5, preferably 0.4 eV or more. If the energy gap of the host material of the first luminescent layer 3 is larger or less than 0.4 eV, the difference in the affinity level between the second luminescent layer 5 and the charge barrier layer 4 becomes large. For this reason, the supply of electrons to the first light-emitting layer 3 becomes insufficient, and it may be difficult to obtain good white light emission. Specifically, the energy gap of the host material of the first light emitting layer 3 is preferably 1.8 to 2.8 eV, and the energy gap of the host material of the second light emitting layer 5 is preferably 2.2 to 3.3 eV. That's right.

 When the dopant of the first light emitting layer 3 is a red dopant and the dopant of the second light emitting layer 5 is a blue dopant, the first light emitting layer 3 emits red light and the second light emitting layer 5 emits blue light. In addition to emitting light, satisfying the above requirements can provide well-balanced white light emission.

 [0028] The reason why it is preferable that the energy of the host material of the first light-emitting layer is smaller than the energy of the host material of the second light-emitting layer is not clear, but can be considered as follows.

 Since the color that makes it difficult to increase the emission intensity is blue, excitons are generated mainly using this blue to emit light. Therefore, blue is preferably located on the cathode side of the electron barrier layer. Then, red is arranged on the anode side of the electron barrier layer. When such an arrangement is made, excitons are generated in the second light emitting layer (blue), which is the negative side of the electron barrier layer, and this blue shines well. Since the second light emitting layer has a wider energy gap than the first light emitting layer, the energy is transferred to the first light emitting layer side. As a result, the red color of the second light emitting layer also shines.

 Note that the element configuration of the present embodiment is not limited to FIG. 1, and may be, for example, the following configuration.

 1.Anode Z 1st light emitting layer Z charge barrier layer Z 2nd light emitting layer Z cathode

2.Anode Z hole transport layer Z 1st light emitting layer Z charge barrier layer Z 2nd light emitting layer Z cathode 3.Anode Z 1st light emitting layer Z charge barrier layer Z 2nd light emitting layer Z electron transport layer Z cathode

4.Anode Z hole transport layer Z 1st light emitting layer Z charge barrier layer Z 2nd light emitting layer Z electron transport layer Z negative electrode

 5.Anode Z hole injection layer Z hole transport layer Z 1st light emitting layer Z charge barrier layer Z 2nd light emitting layer z electron transport layer Z cathode

 6.Anode Z hole injection layer Z hole transport layer Z 1st light emitting layer Z charge barrier layer Z 2nd light emitting layer z electron transport layer Z electron injection layer Z cathode

 [0030] Among these configurations, it is preferable to have a hole transport layer.

 In addition to the layers described above, other organic layers or inorganic layers can be interposed. The intervening layer is not limited as long as it can transport electrons and holes. When it is in the light extraction direction, it is preferably transparent.

 [0031] Embodiment 2

 The organic EL device according to Embodiment 2 includes an anode, a first light emitting layer, a charge barrier layer, a second light emitting layer, a third light emitting layer, and a cathode laminated in this order. The first light emitting layer, the second light emitting layer, and the third light emitting layer force each contain a host material and a dopant.

 Here, the host material of the first light emitting layer becomes the hole transporting material force, and the host materials of the second light emitting layer and the third light emitting layer become the electron transporting material. Furthermore, the energy gap of the host material of the first light emitting layer is smaller than the energy gap of the host material of the second light emitting layer! /. The charge barrier layer is hole transporting. Further, the affinity leveler of the charge barrier layer is preferably 0.2 eV or more smaller than the affinity level of the host material of the second light emitting layer.

 Furthermore, the ionization potential (Iel) of the charge barrier layer and the ionization potential (Ihl) force of the host material of the first light-emitting layer satisfy the following relationship (1).

 IeKIhl + O. 1 (eV) · · · (1)

FIG. 3 is a diagram illustrating an example of the configuration of the organic EL element according to the second embodiment.

The organic EL device 20 shown in FIG. 3 is formed by laminating an anode hole transport layer 2, a first light emitting layer 3, a charge barrier layer 4, a second light emitting layer 5, a third light emitting layer 8, an electron transport layer 6 and a cathode 7. Has a structure. That is, the configuration is the same as that of the first embodiment except that the third light emitting layer 8 is formed. The third light emitting layer 8 also contains a host material and a dopant. The host material of the third light emitting layer 8 is Like the second light emitting layer 5, it is an electron transporting material.

In this element 20, for example, the first light emitting layer 3 has a first dopant as a red dopant, the second light emitting layer 5 has a blue dopant, and the third light emitting layer 8 has a green dopant as a first dopant. By making the light emitting layer 3 red light emission, the second light emitting layer 5 blue light emission, and the third light emitting layer 8 green light emission, white light emission with further excellent color rendering can be obtained. Usually, the energy gap of blue dopant is about 2.8 eV, the energy gap of green dopant is about 2.5 eV, and the energy gap of red dopant is about 2. OeV.

 In the present embodiment, the first light emitting layer 3, the charge barrier layer 4, and the second light emitting layer 5 do not necessarily have the relationship as in the first embodiment. This is because the amount of electrons injected into the first light emitting layer 3, the charge barrier layer 4, and the second light emitting layer 5 is limited by forming the third light emitting layer 8. In particular, since the third light emitting layer is doped with a green dopant, electrons are trapped by this green dopant, and electron injection into the second light emitting layer is controlled.

 However, in order to further improve the performance of the device, the ionization potential, the power level, and the energy gap of the host material of the first light emitting layer 3, the charge barrier layer 4 and the host material of the second light emitting layer 5 are Preferred to have the same relationship as one.

As in the first embodiment, the element configuration of the present embodiment is not limited to FIG. 3. For example, a configuration in which the third light emitting layer is formed on the element configuration 16 illustrated in the first embodiment may be used. Alternatively, a plurality of charge barrier layers may be stacked.

In the above embodiment, preferably, the host material strength of the first light emitting layer is a compound represented by the following formula (1), and the dopant of the first light emitting layer is a compound having a fluoranthene skeleton or a perylene skeleton. .

 X-(Y) n (1)

 (In the formula, X is a condensed aromatic ring group having 3 or more carbon rings,

 Υ is a group selected from a substituted or unsubstituted aryl group, a substituted or unsubstituted dialyl amino group, a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group,

η is an integer of 1 to 6, and when η is 2 or more, Υ may be the same or different. ) [0037] More preferably, the host material of the first light emitting layer has 4 or more condensed rings. Preferably, the host material of the second light emitting layer has 3 or less condensed rings.

 As described above, the embodiment of the present invention has been described. In the element of the present invention, the anode, the hole transporting first light emitting layer, the charge barrier layer, the electron transporting second light emitting layer, and the cathode are arranged in this order. It is constructed by laminating. With such a configuration, an organic EL device having color rendering properties, high luminous efficiency, and little chromaticity change can be obtained. In addition, the element of the present invention is characterized in that the chromaticity change of light emission is small even when the driving conditions (driving voltage, etc.) of the element are changed.

 [0039] Embodiment 3

 The full-color light emitting device according to Embodiment 3 of the present invention includes the organic EL element of the present invention that emits white light and a color filter.

 FIG. 4 is a diagram illustrating an example of the configuration of the full-color light emitting device according to the third embodiment.

 The full-color light emitting device 100 shown in FIG. 4 is provided with first, second, and third (white) organic EL elements 120, 130, and 140 force S on a support substrate 110, and the light of these elements 120, 130, and 140 is provided. First, second, and third (red, green, and blue) color filters 122, 132, and 142 are arranged on the extraction side (indicated by arrows) so as to face these elements 120, 130, and 140, respectively. . The color filters 122, 132, 142 are formed on the transparent substrate 150.

 The light emitted from the organic EL element 120 is converted to red light by the color filter 122 and extracted outside, and the light emitted from the organic EL element 130 is converted to green light by the color filter 132 and extracted to the outside. The light emitted from the element 140 is converted into blue light by the color filter 142 and extracted outside to obtain a full color.

 [0041] Between the organic EL elements 120, 130, and 140 and the color finoletas 122, 132, and 142, the organic EL element is prevented from being deteriorated by oxygen, moisture, or other volatile components contained in the environment or the color filter. A sealing layer or the like may be provided. Specific examples include transparent inorganic compound layers such as SiOxNy, AlOxNy, and SiAlOxNy, and those laminated with these transparent inorganic compound layers and a transparent resin or sealing liquid.

 [0042] Examples of the color filters 122, 132, 142 include, for example, the following dyes only or those in a solid state in which the dyes are dissolved or dispersed in a binder resin.

[0043] Red (R) dye: Perylene pigment, lake pigment, azo pigment, etc. Green (G) dyes: Halogen polysubstituted phthalocyanine pigments, halogen polysubstituted copper phthalocyanine pigments, trifelmethane basic dyes, etc.

 Blue (B) dye: Copper phthalocyanine pigment, indanthrone pigment, indophenol pigment, cyanine pigment, etc.

[0044] On the other hand, the binder resin is preferably a transparent material (visible light transmittance of 50% or more). For example, transparent rosin (polymer) such as polymethylmetatalylate, polyatalylate, polycarbonate, polybulal alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose, canoleboxymethinoresolerose, etc., or a photolithography method Examples of the photosensitive resin that can be applied include photo-curing resist materials having a reactive vinyl group such as acrylic acid-based or methacrylic acid-based resins. When using the printing method, printing ink (medium) using a transparent resin such as polyvinyl chloride resin, melamine resin, or phenol resin is selected.

 [0045] When the color filter mainly has a coloring power, it is formed by vacuum deposition or sputtering through a mask having a desired color filter pattern. On the other hand, when the color filter is composed of a coloring material and a binder resin, the coloring material and the above color filter are formed. Oils and resists are mixed, dispersed or solubilized, formed into a film by a method such as spin coating, roll coating, or casting, and patterned with a desired color filter pattern by a photolithography method, or by a method such as printing. It is common to pattern with a desired color filter pattern.

[0046] The film thickness and transmittance of each of the color filters 122, 132, 142 are preferably as follows.

 R: film thickness 0.5 to 5.0 111 (transmittance 50% or more 761011111),

 0: Film thickness 0.5-5.O / z m (Transmittance 50% or more Z545nm),

 8: Film thickness 0.2-5 (Transmittance 50% or more Z460nm).

 In this embodiment, when providing a full-color light emitting device that emits light of three primary colors of red, green, and blue, a black matrix can be used to improve the contrast ratio.

Hereinafter, the charge barrier layer, the first light emitting layer, and the second light emitting layer (third light emitting layer), which are characteristic parts of the organic EL device of the present invention, will be mainly described. For other organic layers, inorganic compound layers, positive electrodes, cathodes, and the like and the manufacturing method, general configurations can be adopted. [0049] 1. Charge barrier layer

The charge barrier layer is preferably at least 10 ^_5 cm ² ZV ′ seconds or more when an electric field of hole mobility of 10 ⁴ to 10 ⁷ VZcm is applied from the viewpoint that it is difficult to become a barrier against holes.

 The thickness of the charge barrier layer is not particularly limited, but is preferably 0.1 to 50 nm. More preferably, the thickness is 0.1 to 20 nm.

 [0050] Various organic compounds and inorganic compounds can be used for the charge barrier layer. As the organic compound, a tertiary amine compound, a force rubazole derivative, a compound containing a nitrogen-containing heterocyclic ring, a metal complex, or the like can be used. Inorganic compounds include Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, K, Cd, Mg, Si, Ta, Ge, Sb, Zn, Cs, Eu, Y, Ce, W, Zr , La, Sc, Rb, Lu, Ti, Cr, Ho, Cu, Er, Sm, W, Co, Se, Hf, Tm, Fe, Nb and other metal oxides, nitrides, complex oxides, Sulfides, fluorides, etc. can be used.

 [0051] In addition, from the viewpoint that the charge barrier layer is unlikely to be a barrier against holes, the organic compounds described below that are usually used as a hole transport layer in an organic EL device are preferable.

Specific examples include triazole derivatives (see US Pat. No. 3,112,197), oxadiazole derivatives (see US Pat. No. 3,189,447), imidazole derivatives (Japanese Patent Publication No. 37-16096). Polyarylalkane derivatives (US Pat. Nos. 3,615,402, 3,820,989, 3,542,544, JP-B-45-555) 51-10983, JP-A 51-93224, 55-17105, 56-4148, 55-108667, 55-156953, 56-36656 Pyrazoline derivatives and pyrazolone derivatives (US Pat. Nos. 3,180,729 and 4,278,746, JP-A-55-88064, 55-88065) No. 49-105537, No. 55-51086, No. 56-80051, No. 56-88141, No. 57-45545, No. 54-11 263 7), 55-74546, etc.), Phylenediamine derivatives (US Pat. No. 3,615,404, JP-B 51-10105, 46-3712, 4 7- JP 25336, JP 54-53435, 54-110536, 54-1 19925), arylamine derivatives (US Pat. Nos. 3,567,450, 3,180,703, 3,240,597, 3,658, No. 520, No. 4, 232, 103, No. 4, 175, 961, No. 4, 012, 37 6, Akira Ito, No. 49-35702, No. 39 — See 27577, JP 55-144 250, 56-119132, 56-22437, West German Patent 1,110,518, etc.), amino-substituted chalcone derivatives (US) Patent No. 3,526,501, etc.), oxazole derivatives (disclosed in US Pat. No. 3,257,203, etc.), styrylanthracene derivatives (see JP 56-46234, etc.) Fluorene derivatives (see Japanese Patent Laid-Open No. 54-110837), hydrazone derivatives (US Pat. No. 3,717,462, Japanese Patent Laid-Open No. 54-59143, 55-52063, 55 No. 52 064, No. 55-46760, No. 55-85495, No. 57-11350, No. 57-148749, JP-A-2-311591, etc.), Stilbene derivatives (JP-A) 61-210363, 61-228451, 61-14642, 61-72255, 62-47646, 62-36674, 62-10652, 62-30255, 60-93455, 60-94462, 60-174749, 60-175052, etc.), silazane derivatives (US Pat. No. 4,950,950) Description), polysilane-based (JP-A-2-204996), aniline-based copolymer (JP-A-2-282263), and JP-A-1-211399 (Especially thiophene oligomer).

 [0052] In addition, a Borhuylin compound (disclosed in JP-A-63-29556965), an aromatic tertiary amine compound and a styrylamine compound (US Pat. No. 4,127,412) Kaisho 53-27033, 54-58445, 54-149634, 54-64299, 55-79450, 55-144250, 56-11913 2 61-295558, 61-98353, 63-295695, etc.) can also be used. In particular, it is preferable to use an aromatic tertiary amine compound.

 [0053] Furthermore, a compound represented by the following formula is also preferable.

[Chemical 4]

式中、 Ar 〜A ⁴は、それぞれ独立に、置換もしくは無置換の核炭素数 6〜50の ァリール基であり、 R²¹及び R²²は、それぞれ独立に、水素原子、置換もしくは無置換 の核炭素数 6〜50のァリール基、炭素数 1〜50のアルキル基であり、 m、 nは 0〜4の 整数である。

In the formula, Ar to A ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 50 nuclear carbon atoms, and R ²¹ and R ²² are each independently a hydrogen atom, a substituted or unsubstituted nucleus. An aryl group having 6 to 50 carbon atoms and an alkyl group having 1 to 50 carbon atoms, and m and n are integers of 0 to 4.

 [0054] As the aryl group having 6 to 50 nuclear carbon atoms, a phenyl, naphthyl, biphenyl, terphenyl, phenanthryl group and the like are preferable. In addition, the aryl group having 6 to 50 nuclear carbon atoms may be further substituted with a substituent. Preferred substituents include alkyl groups having 1 to 6 carbon atoms (methyl group, ethyl group, isopropyl group, n -Propyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group, etc.), and an amino group substituted with an aryl group having 6 to 50 carbon atoms.

 Examples of the alkyl group having 1 to 50 carbon atoms include methyl group, ethyl group, isopropyl group, n-propyl group, sbutyl group, tbutyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group, and the like. Is preferred.

 [0055] Further, there are two condensed aromatic rings described in US Pat. No. 5,061,569 in the molecule, for example, 4,4,1bis (N— (1-naphthyl) N phenol. -Lumino) biphenyl (NPD), 4, 4 ', 4 "tris (N- (3 -Methylphenol) -N-phenolamino) triphenylamine (MTDATA).

[0056] A light emitting material may be added to the charge barrier layer. As a result, light emission including light of various components can be obtained. For example, when the light emitting layer is a first light emitting layer 3 and a second light emitting layer 5 as in Embodiment 1, the dopant of the first light emitting layer 3 is a red dopant and the dopant of the second light emitting layer is blue. The light emitting material of the dopant and charge barrier layer is a green dopant. That is, light emission However, when blue is the weakest, blue is placed in the most shining area, and with high visibility, green is placed in the next most shining area. This is because when the green light emission shifts, the color shift is immediately noticeable when a person sees it, and a well-balanced white color cannot be achieved. Since red emits light by the power of charge injection, energy transfer from blue and green, it may be at the position of the first light emitting layer. This arrangement can achieve a three-wavelength white color that is well balanced in efficiency and resists color shifts. As the light emitting material, dopants used in each light emitting layer described later can be used.

 When the charge barrier layer includes a light emitting material, the affinity level and ion potential of the charge barrier layer are the affinity level and ionization potential of the host material of the charge barrier layer.

[0057] 2. First light emitting layer

 In view of the energy gap described above, the first light emitting layer is preferably a yellow to orange or red light emitting layer. The yellow to orange or red light emitting layer is a light emitting layer having a maximum emission wavelength of 550 to 650 nm. The light emitting layer is preferably composed of a host material and a yellow to orange or red dopant.

 As the host material, a compound represented by the following formula is used.

 X- (Y) n

 (In the formula, X is a condensed aromatic ring group having 3 or more carbon rings,

 Υ is a group selected from a substituted or unsubstituted aryl group, a substituted or unsubstituted dialyl amino group, a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group,

 η is an integer of 1 to 6, and when η is 2 or more, Υ may be the same or different. ) X It is a group containing one or more skeletons selected from dibenzopyrene, dibenzofluoranthene, and isanaphthylfluoranthene. More preferably, it contains a naphthacene skeleton or an anthracene skeleton.

Υ is preferably an aryl group or diarylamino group having 12 to 60 carbon atoms, and more preferably. Or an aryl group having 12 to 20 carbon atoms or a diarylamino group having 12 to 40 carbon atoms. n is preferably 2.

 Preferably, the compound represented by the formula (1) is a naphthacene derivative represented by the following formula (4).

 [Chemical 5]

(4) In formula (4), (^ to ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 nuclear carbon atoms. , Amino group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, substituted or unsubstituted Substituted aryl aryl group having 6 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, or substituted or unsubstituted nuclear atoms 5 Represents ~ 20 heterocyclic groups, which may be the same or different.

More preferably, QQ ² , Q ³ and Q in the naphthacene derivative represented by the above formula (4)

^A compound in which at least one of ⁴ is an aryl group.

[0061] More preferably, the naphthacene derivative represented by the formula (4) is a compound represented by the following formula (5).

[Chemical 6]

(In the formula (5), Q ^{3 to} Q ¹² , Q ¹⁰¹ to Q ¹⁰⁵ , Q ^{201 to} Q ² ° ⁵ each independently represents the same group as Q ^{3 to} Q ¹² in the general formula (1), These two, which may be the same or different, may be bonded to each other to form a ring.

[0062] More preferably, at least one alkyl group of Q ^lcn, Q ^105, Q ²⁰¹ and Q ^2G5 in naphthacene derivative represented by the formula (5), Ariru group, an amino group, an alkoxy group, § Rirokishi A group, an alkylthio group, an arylthio group, an alkyl group, an aralkyl group or a heterocyclic group, which may be the same or different.

[0063] As a yellow to orange or red dopant, a fluorescent compound having at least one fluoranthene skeleton or perylene skeleton can be used, and examples thereof include compounds represented by the following formulas [2] to [18]. .

[0064] [Chemical 7]

Sl7C090 / .00Zdf / X3d 9068Cl / .00Z OAV

(式〔2〕〜〔16〕式中、 X^X^は、それぞれ独立に、水素原子、直鎖、分岐もしくは 環状の炭素原子数 1〜20のアルキル基、直鎖、分岐もしくは環状の炭素原子数 1〜 20のアルコキシ基、置換もしくは無置換の炭素原子数 6〜30のァリール基、置換もし くは無置換の炭素原子数 6〜30のァリールォキシ基、置換もしくは無置換の炭素原 子数 6〜30のァリールアミノ基、置換もしくは無置換の炭素原子数 1〜30のアルキル アミノ基、置換もしくは無置換の炭素原子数 7〜30のァリールアルキルアミノ基又は 置換もしくは無置換炭素原子数 8〜30のァルケ-ル基であり、隣接する置換基及び 〜 ^は結合して環状構造を形成して 、てもよ 、。隣接する置換基がァリール基の 時は、置換基は同一であってもよい。 )

(In the formulas [2] to [16], X ^ X ^ is independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic carbon. Alkoxy group having 1 to 20 atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted carbon atom number 6-30 aryl amino groups, substituted or unsubstituted alkyl amino groups having 1 to 30 carbon atoms, substituted or unsubstituted aryl amino groups having 7 to 30 carbon atoms, or substituted or unsubstituted carbon atoms 8 to 30 alkenyl groups, adjacent substituents and ~ ^ may be bonded to form a cyclic structure, and when adjacent substituents are aryl groups, the substituents are the same. Good.)

 The compounds of the formulas [2] to [16] preferably contain an amino group or a alkenyl group.

[0065] [Chemical 8]

[0066] In the formulas [17] and [18], X ^{21 to} X ²⁴ are each independently an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. X ²¹ and X ²² and / or X ²³ and X ²⁴ may be bonded via a carbon-carbon bond or —O— or —S—.

X ^{25 to} X ³⁶ are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted group. Aryl group having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted aryl group with 6 to 30 carbon atoms, substituted Alternatively, an unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 7 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 8 to 3 carbon atoms

An alkenyl group of 0, adjacent substituents and x ^{25 to} x ³⁶ may be bonded to form a cyclic structure;

It is preferred that at least one of the substituents X ^{25 to} X ³⁶ in each formula contains an amine or alkenyl group.

 Indenoperylene derivatives of the formulas [13] and [14] are preferred.

[0067] The fluorescent compound having a fluoranthene skeleton preferably contains an electron donating group in order to obtain high efficiency and a long lifetime. The preferred electron donating group is a substituted or unsubstituted arylene amino group. It is. Further, the fluorescent compound having a fluoranthene skeleton preferably has 5 or more condensed rings, and more preferably 6 or more. This is because the fluorescent compound exhibits a fluorescent peak wavelength of 540 to 70 Onm, and the light emission from the blue light emitting material and the fluorescent compound is superposed and white.

 The above-mentioned fluorescent compound is preferable because it has a plurality of fluoranthene skeletons, since the emission color is in a yellow to orange or red region.

 In particular, the indenoperylene derivative is a dibenzotetraphenyl perifuranthene derivative.

 [0068] The thickness of the first light emitting layer is preferably 1 to 50 nm, more preferably 5 to 50 nm. If it is less than lnm, the luminous efficiency may decrease, and if it exceeds 50 nm, the drive voltage may increase.

 [0069] 3. Second light emitting layer

 Regarding the luminescent color, the second light emitting layer is preferably a blue light emitting layer in view of the energy gap. Preferably, the peak wavelength of blue light emission is 450 to 500 nm.

Examples of dopants that can be used in the second light emitting layer include arylene compounds and Z or styrylamine compounds, anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, taricene, fluorescein, perylene, lidar perylene, and naphthaperylene. , Perinone, lid-perinone, naphtha-perinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxazirazole, aldazine, bisbenzoxazoline, bisstyryl, Pyrazine, cyclopentagen, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diamino force rubazole, pyran, thiopyran, polymethine, merocyanine, imidazole chelate oxinoid compound, quinacridone , Rubrene and fluorescent dyes, but are not limited thereto.

 In the organic EL device of the present invention, the second light emitting layer preferably contains an arylamine compound and Z or styrylamine compound.

 Examples of arylamine compounds include compounds represented by the following general formula (A), and examples of styrylamine compounds include compounds represented by the following general formula (B).

[Chemical 9]

 (A)

[In the general formula (A), Ar represents a fuel, a bifuel, a terpheal, a stilbene, a distil

 8

Ar and Ar are each a hydrogen atom or a carbon number.

 9 10

Is an aromatic group of 6 to 20, and Ar to Ar may be substituted. p, is an integer from 1 to 4

 9 10

It is. More preferably, Ar and Z or Ar are substituted with a styryl group. ]

 9 10

 Here, the aromatic group having 6 to 20 carbon atoms is preferably a phenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, a terphenyl group, or the like.

[Chemical 10]

[In the general formula (B), Ar to Ar are optionally substituted aryl groups having 5 to 40 nuclear carbon atoms. It is. q is an integer from 1 to 4. ]

 Here, aryl groups having 5 to 40 nuclear atoms include phenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, coloninole, biphenyl, terphenyl, pyrrolyl, furanyl, thiophenyl, benzothiophenyl, oxadiazolyl, Preference is given to diphenylanthracenyl, indolyl, carbazolyl, pyridyl, benzoquinolyl, fluoranthenyl, isenaftfluoroolturyl, stilbene and the like. In addition, the aryl group having 5 to 40 nucleus atoms may be further substituted with a substituent. Examples of the preferred substituent are alkyl groups having 1 to 6 carbon atoms (ethyl group, methyl group, isopropyl group, n —Propyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group, etc.), alkoxy group having 1 to 6 carbon atoms (ethoxy group, methoxy group, isopropoxy group, n— Propoxy group, s-butoxy group, t-butoxy group, pentoxy group, hexyloxy group, cyclopentoxy group, cyclohexyloxy group, etc.), aryl group having 5-40 nuclear atoms, aryl group having 5-40 nuclear atoms An ester group having an aryl group having 5 to 40 nuclear atoms, an ester group having an alkyl group having 1 to 6 carbon atoms, a cyan group, a nitro group, a halogen atom (chlorine, bromine) Iodine, etc.) and the like.

 As a host material that can be used for the second light emitting layer, a compound having an anthracene center skeleton and a structure represented by the following formula (19) is preferable.

[Chemical 11]

(In the formula, A and A are each independently a substituted or unsubstituted aromatic group having 6 to 20 nuclear carbon atoms.

 1 2

A group derived from a group ring. R to R are each independently a hydrogen atom, substituted or absent.

 1 8

Substituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted hetero atom having 5 to 50 nuclear atoms Aryl group, substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted A aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 carbon atoms, a substituted or unsubstituted aryl atom group having 5 to 50 carbon atoms, a substituted or unsubstituted carbon atom having 1 to 50 carbon atoms An alkoxycarbonyl group, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group or a hydroxyl group. [0074] The aromatic rings of A and A may be substituted with one or more substituents. This replacement

 1 2

 The group is a substituted or unsubstituted aryl group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted group. An unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted alkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted nucleus; Arylthio group having 5 to 50 atoms, substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, substituted or unsubstituted silyl group, carboxyl group, halogen atom, cyano group, nitro group and hydroxyl group Power is chosen.

[0075] When the aromatic rings of A and A are substituted with two or more substituents, the substituents are the same

 1 2

 The adjacent substituents may be bonded to each other to form a saturated or unsaturated cyclic structure.

[0076] In the formula (19), A and A are preferably different from each other.

 1 2

 [0077] Further, compounds represented by the following (i) to (ix) are preferred:

[0078] An asymmetric anthracene represented by the following general formula (i):

 [Chemical 12]

[In the formula, Ar is a substituted or unsubstituted condensed aromatic group having 10 to 50 nuclear carbon atoms. Ar is a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms.

X ¹ , X ² and X ³ are each independently a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, substituted Or an unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted nuclear atom. 5 to 50 aryloxy group, substituted or unsubstituted nuclear atom 5 to 50 arylol group, substituted or unsubstituted alkoxycarbon group having 1 to 50 carbon atoms, carboxyl group, halogen atom, cyano group , Nitro group, hydroxyl group.

a, b and c are each an integer of 0-4. Incidentally, a, when b and c is 2 or more, X ¹ the mechanic, X ² together, X ³ together may be the same or different.

 n is an integer of 1 to 3. When n is 2 or more, the values in [] may be the same or different. )

 [0080] An asymmetric monoanthracene derivative represented by the following general formula (ii):

 [Chemical 13]

(i i)

[0081] (wherein Ar ¹ and Ar ² are each independently a substituted or unsubstituted aromatic ring group having 6 to 50 nuclear carbon atoms, and m and n are each an integer of 1 to 4) However, if m = n = l and the bonding positions of Ar ¹ and Ar ^{2 to} the benzene ring are symmetrical, Ar ¹ and Ar ² are not the same m or n is an integer from 2 to 4 In the case of, m and n are different integers.

~! ^ Are independently hydrogen atoms, substituted or unsubstituted 6 to 50 nuclear carbon atoms. Aromatic ring group, substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group, substituted or Unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted nuclear atoms 5 An arylcarbothio group of ˜50, a substituted or unsubstituted alkoxycarbon group having 1 to 50 carbon atoms, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, and a hydroxyl group. )

[0082] An asymmetric pyrene derivative represented by the following general formula (iii):

 [Chemical 14]

[In the formula, Ar and Ar are each a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms.

 L and L are each a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted fluorenylene group, or a substituted or unsubstituted dibenzosilolylene group.

 m is an integer from 0 to 2, n is an integer from 1 to 4, s is an integer from 0 to 2, and t is an integer from 0 to 4. L or Ar is bonded to any of the 1-5 positions of pyrene, and L or Ar, is bonded to any of the 6-10 positions of pyrene.

 However, when n + t is an even number, Ar, Ar ', L, and V satisfy the following (1) or (2).

(1) Ar ≠ Ar ′ and Z or L ≠ L ′ (where ≠ indicates a group having a different structure.) (2) When Ar = Ar and L = L

 (2-1) m ≠ s and Z or n ≠ t, or

 (2-2) When m = s and n = t,

 (2-2-1) Whether L and L ′, or pyrene are bonded to different bond positions on Ar and Ar, respectively,

 (2-2-2) When L and L 'or pyrene are bonded at the same bonding position on Ar and Ar,

 The substitution positions of L and L 'or Ar and Ar in pyrene are not the 1st and 6th positions or the 2nd and 7th positions. ]

[0084] An asymmetric anthracene derivative represented by the following general formula (iv):

 [Chemical 15]

[In the formula, A ¹ and ¹ are each independently a substituted or unsubstituted condensed aromatic ring group having 10 to 20 nuclear carbon atoms.

Ar ¹ and Ar ² are each independently a hydrogen atom or a substituted or unsubstituted aromatic ring group having 6 to 50 nuclear carbon atoms.

~! ^ Is independently a hydrogen atom, a substituted or unsubstituted aromatic ring group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, a substituted or unsubstituted Is an unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group, Substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 carbon atoms, substituted or unsubstituted nuclear atom An arylcarbothio group having 5 to 50 carbon atoms, a substituted or unsubstituted carbon group having 1 to 50 carbon atoms, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or a hydroxyl group. .

Ar ² , R ⁹ and R ¹⁰ may be plural or adjacent to each other to form a saturated or unsaturated cyclic structure.

 However, in the general formula (1), a group that is symmetrical with respect to the XY axes shown on the anthracene is not bonded to the 9th and 10th positions of the central anthracene. )

[0086] An anthracene derivative represented by the following general formula (V):

 [Chemical 16]

[0087] (wherein 1 ^ to 1 ^ ^{1 ()} are each independently a hydrogen atom, alkyl group, cycloalkyl group, optionally substituted aryl group, alkoxyl group, aryloxy group, alkylamino group, alkke group. A-group, an arylamino group or an optionally substituted heterocyclic group, a and b each represent an integer of 1 to 5, and when they are 2 or more, R ¹ or R ² are In each case, they may be the same or different, and R ¹ or R ² may be bonded to each other to form a ring, or R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ And R ⁸ , R ⁹ and R ^1C) may be bonded to each other to form a ring. L ¹ represents a single bond, —O—, —S—, —N (R) — (R represents an alkyl group or an aryl group which may be substituted), an alkylene group or an arylene group. )

[0088] An anthracene derivative represented by the following general formula (vi): [Chemical 17]

[0089] (wherein R ¹¹ to! ^ Are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxyl group, an aryloxy group, an alkylamino group, an arylamino group, or Cd, e and f each represent an integer of 1 to 5, and when they are 2 or more, R ¹¹ , R ¹² , R ^16, or R ¹⁷ In each case, they may be the same or different, and R ¹¹ , R ¹² , R ^16, or R ¹⁷ may combine to form a ring, or R ¹³ and R ¹⁴ , R ¹⁸ and R ¹⁹ may be bonded to each other to form a ring L ² is a single bond, —O—, 1 S—, — N (R) — (R is an alkyl group or an optionally substituted aryl group. Represents an alkylene group or an arylene group.

[0090] A spirofluorene derivative represented by the following general formula (vii):

 [Chemical 18]

(In the formula, A ^{5 to} A ⁸ each independently represents a substituted or unsubstituted biphenyl group or a substituted or unsubstituted naphthyl group.) [0092] A condensed ring-containing compound represented by the following general formula (viii):

 [Chemical 19]

[In the formula, A ^{9 to} A ″ are each a single bond or a substituted or unsubstituted arylene group having 6 to 50 nuclear carbon atoms, and A ^{12 to} A ¹⁴ are a hydrogen atom or a substituted or unsubstituted group, respectively. An aryl group having 6 to 50 nuclear carbon atoms R ^{21 to} R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or 1 to 6 carbon atoms. An alkoxyl group having 5 to 18 carbon atoms, an aralkyloxy group having 7 to 18 carbon atoms, an arylamino group having 5 to 16 carbon atoms, a nitro group, a cyano group, an ester group having 1 to 6 carbon atoms or a halogen atom. And at least one of A ^{9 to} A ¹⁴ is a group having three or more condensed aromatic rings.

 [0094] A fluorene compound represented by the following general formula (ix).

 [Chemical 20]

[In the formula, R and R are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or

 1 2

It represents an unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted amino group, a cyano group or a halogen atom. Different fluorene groups R bonded to each other, R may be the same or different, and the same fluorene group

1 2

 R to bind to

 1 and R

 2 may be the same or different. R

 3 and R

 4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and R bonded to different fluorene groups , R may be the same or different, the same

 3 4

 R and R bonded to the fluorene group may be the same or different. Ar and

 3 4 1

Ar is a substituted or unsubstituted condensed polycyclic aromatic group having a total of 3 or more benzene rings.

2

 Represents a condensed polycyclic heterocyclic group in which the total of the benzene ring and the heterocyclic ring is bonded to the fluorene group with 3 or more substituted or unsubstituted carbons. Ar and Ar may be the same or different.

 1 2

 May be. n represents an integer of 1 to 10. )

 [0096] Among the above host materials, anthracene derivatives are preferable, monoanthracene derivatives are more preferable, and asymmetric anthracene is particularly preferable.

 [0097] The blue dopant is preferably at least one selected from a styrylamine, an amine-substituted styryl compound, and a fused aromatic ring-containing compound. At that time, the blue dopant is composed of a plurality of different compound forces. Examples of the styrylamine and amine-substituted styryl compound include a compound force represented by the following formula [20] or [21]. The above condensed aromatic ring-containing compound may be represented by the following formula [22], for example. Compounds.

 [Chemical 21]

[In the formula, Ar \ Ar ³² and Ar ³³ each independently represent a substituted or unsubstituted aromatic group having 6 to 40 carbon atoms, and p represents an integer of 1 to 3. Preferably, at least one of Ar ³¹ , Ar ³² and Ar ³³ contains a styryl group. ]

[0098] [Chemical 22]

[In the formula, Ar ⁴¹ and Ar ⁴² are each independently an arylene group having 6 to 30 carbon atoms, E ¹ and H ² are each independently an aryl group or alkyl group having 6 to 30 carbon atoms, It represents a hydrogen atom or a cyan group, and q represents an integer of 1 to 3. U and Z or V are substituents containing an amino group, and the amino group is preferably an aryl amino group. ]

[0099] [Chemical 23]

^(AB [ _{2 2} ]

[In the formula, A is an alkyl group or alkoxy group having 1 to 16 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 6 to 30 carbon atoms, Alternatively, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, B represents a condensed aromatic ring group having 10 to 40 carbon atoms, and r represents an integer of 1 to 4. ]

[0100] As the green dopant, the same arylamine compound and Z or styrylamine compound as the blue dopant described above can be used. Preferably, the peak wavelength of green light emission is 500 to 550 nm.

 Preferably, an aromatic amine compound represented by the formula (1) can be used as a green dopant.

 [Chemical 24]

[0101] 式（1)において、 ^〜A²は、それぞれ独立に、水素原子、置換もしくは無置換の炭 素数 1〜10 (好ましくは、炭素数 1〜6)のアルキル基、置換もしくは無置換の核炭素 数 5〜50 (好ましくは、核炭素数 5〜： LO)のァリール基、置換もしくは無置換の核炭素 数 3〜20 (好ましくは、核炭素数 5〜： LO)のシクロアルキル基、置換もしくは無置換の 炭素数 1〜10 (好ましくは、炭素数 1〜6)のアルコキシ基、置換もしくは無置換の核 炭素数 5〜50 (好ましくは、核炭素数 5〜： LO)のァリールォキシ基、置換もしくは無置 換の核炭素数 5〜50 (好ましくは、核炭素数 5〜20)のァリールアミノ基、置換もしく は無置換の炭素数 1〜10 (好ましくは、炭素数 1〜6)のアルキルアミノ基、又はハロ ゲン原子を表す。

[0101] In Formula (1), ^ to A ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a substituted or unsubstituted group. An aryl group having 5 to 50 nuclear carbon atoms (preferably 5 to LO), a substituted or unsubstituted cycloalkyl group having 3 to 20 nuclear carbon atoms (preferably 5 to LO). A substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a substituted or unsubstituted nuclear carbon atom having 5 to 50 carbon atoms (preferably a nuclear carbon number 5 to LO). Group, substituted or unsubstituted nuclear carbon group having 5 to 50 (preferably, nuclear carbon number 5 to 20) aryl group, substituted or unsubstituted carbon 1 to 10 (preferably 1 to 6 carbon atoms) ) Represents an alkylamino group or a halogen atom.

[0102] Examples of the substituted or unsubstituted alkyl group of A to A ^2, for example, a methyl group, Echiru group, a propyl group, an isopropyl group, butyl group, sec- butyl group, tert- butyl group, pentyl group, to Xyl group, heptyl group, octyl group, stearyl group, 2-phenylisopropyl group, trichloromethyl group, trifluoromethyl group, benzyl group, α-phenoxybenzyl group, a, α-dimethylenobenzenole group, Examples thereof include a, α-methinorefinenobenzylenole group, a, α-ditrifluoromethylbenzyl group, triphenylmethyl group, _α- benzyloxybenzyl group and the like.

[0103] Examples of the substituted or unsubstituted aryl group of A to A ² include, for example, a phenyl group, a 2-methyl furol group, a 3-methyl furol group, a 4-methyl furol group, and a 4-ethyl furyl group. Group, biphenyl group, 4-methylbiphenyl group, 4-ethyl biphenyl group, 4-cyclohexyl biphenyl group, terfel group, 3, 5-dichlorophenyl group, naphthyl group, 5- A methyl naphthyl group, an anthryl group, a pyrenyl group, etc. are mentioned.

[0104] Examples of the substituted or unsubstituted cycloalkyl group of A to A ^2, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornel group, Adama pentyl group and the like.

[0105] The substituted or unsubstituted alkoxy group A to A ^2, for example, a methoxy group, Etoki sheet group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec- butoxy group

Tert-butoxy group, various pentyloxy groups, various hexyloxy groups, etc. [0106] Examples of the substituted or unsubstituted aryloxy group of A ^{1 to} A ² include a phenoxy group, a triloxy group, and a naphthyloxy group.

The substituted or unsubstituted Ariruamino group Hache-eight ^2, for example, Jifue - Ruamino group, ditolylamino group, Jinafuchiruamino group, naphthylene Ruff enyl § amino group and the like. The substituted or unsubstituted alkylamino group Hache-eight ^2, for example, Jimechiruamino group, Jechiruamino group, Kishiruamino group and the like to di.

Examples of the halogen atoms ^ to A ² include a fluorine atom, a chlorine atom, and a bromine atom.

In formula (1), both A ¹ and A ² are not hydrogen atoms.

[0107] In the formula (1), d and e are each an integer of 1 to 5, preferably 1 to 3. When d and e are each 2 or more, the plurality of AA ² may be the same or different, and may be connected to each other to form a saturated or unsaturated ring. H is an integer of 1 to 9, preferably 1 to 3.

[0108] R ¹¹ represents a substituted or unsubstituted secondary or tertiary alkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted secondary or tertiary cycloalkyl group having 3 to 10 carbon atoms. To express.

Examples of the substituted or unsubstituted secondary or tertiary alkyl group having 3 to 10 carbon atoms of R ¹¹ include isopropyl group, tert butyl group, sec butyl group, tert pentyl group, 1-methylbutyl group, 1 -Methylpentyl group, 1,1 'dimethylpentyl group, 1,1' dimethylpropyl group, 1-benzyl-2-phenyl ester, 1-methoxyethyl group, 1-phenyl-1-methylethyl group and the like.

The secondary or tertiary substituted or unsubstituted cycloalkyl group having a carbon number 3-10 of R ^11, for example, a cyclopentyl group, a cyclohexyl group, norbornel group, Adamanchiru group and the like.

In the formula (1), f is an integer of 1 to 9, and preferably 1 to 3. When f is 2 or more, multiple R ^11s may be the same or different!

[0109] R ¹² represents a hydrogen atom, a substituted or unsubstituted carbon group having 1 to: L0 alkyl group (preferably having 1 to 6 carbon atoms), a substituted or unsubstituted aryl group having 5 to 50 nuclear carbon atoms ( Preferably, a nuclear carbon number of 5 to: L0), a substituted or unsubstituted cycloalkyl group having a nuclear carbon number of 3 to 20 (preferably Is a substituted or unsubstituted carbon group having 1 to: LO alkoxy group (preferably 1 to 6 carbon atoms), a substituted or unsubstituted aryloxy group having 5 to 50 nuclear carbon atoms. (Preferably, having 5 to 10 carbon atoms: L0), substituted or unsubstituted arylamino group having 5 to 50 nuclear carbon atoms (preferably 5 to 20 carbon atoms), substituted or unsubstituted carbon having 1 to: L0 represents an alkylamino group (preferably having 1 to 6 carbon atoms) or a halogen atom.

Specific examples of R ¹² substituted or unsubstituted alkyl group, aryl group, cycloalkyl group, alkoxy group, aryloxy group, aryl amino group, alkylamino group and norogen atom are the same as those in Ai to A ² above. Is mentioned.

 In the formula (1), g is an integer of 0 to 8, preferably 0 to 2.

When g is 2 or more, the plurality of R ¹² may be the same or different! /.

 Moreover, in Formula (1), f + g + h is an integer of 2-10, and it is preferable in it being 2-6. As the aromatic amine compound, compounds represented by the formulas (1-1) to (1-7) are more preferable.

[Chemical 25]

/: O1 £ AV ^

[In the formulas (1-1) to (: L-7), AA ² , d, e, R ¹¹ and R ¹² are the same as those in the formula (1). [0111] The thickness of the second light emitting layer is preferably 1 to: LOOnm, more preferably 5 to 50 nm. If it is less than In m, it is difficult to form a light emitting layer, and it may be difficult to adjust the chromaticity, and if it exceeds lOOnm, the drive voltage may increase.

[0112] 4. Third light-emitting layer

 Regarding the emission color, the third light emitting layer is preferably a green light emitting layer in view of the energy gap. Preferably, the peak wavelength of green light emission is 500 to 550 nm. As the host material and dopant of the third light emitting layer, those described above can be used. Host material is first

2 Preferable to be the same material as the light emitting layer.

[0113] The thickness of the third light-emitting layer is preferably 1 to 100 nm, more preferably 5 to 50 nm. If it is less than In m, it is difficult to form a light emitting layer, and it may be difficult to adjust the chromaticity. If it exceeds lOOnm, the drive voltage may increase.

[0114] 5. Other organic layers (1) First organic layer

A hole injection layer, a hole transport layer, an organic semiconductor layer, or the like can be provided as the first organic layer between the anode and the first light emitting layer. The hole injection layer or the hole transport layer is a layer that assists hole injection into the light emitting layer and transports it to the light emitting region, and the ionization energy with high hole mobility is usually as small as 5.5 eV or less. . The hole injection layer is provided to adjust the energy level, for example, to alleviate sudden changes in energy level. Such a hole injecting layer or hole transporting layer is preferably a material that transports holes to the light emitting layer with a lower electric field strength, and further has a hole mobility of, for example, 10 ⁴ to: L0 ⁶ V / cm of when an electric field is applied, at least 10_ ⁶ cm ² ZV,ヽpreferred are those which are second. The material for forming the hole injection layer or the hole transport layer is not particularly limited as long as it has the above-mentioned preferable properties. Conventionally, it has been commonly used as a charge transport material for holes over optical materials. It can be used by selecting any one of those known and used for the hole injection layer of the organic EL element.

Specific examples of the material for forming such a hole injection layer or hole transport layer include, for example, a triazole derivative (see US Pat. No. 3,112,197, etc.), an oxadiazole derivative (US Pat. No. 3, 189, 447, etc.), imidazole derivatives (see Japanese Examined Patent Publication No. 37-1 6096, etc.), polyarylalkane derivatives (US Pat. Nos. 3,615,402, 3,820,989) No. 3,542,544, JP-B 45-555, 51-10983, JP-A 51-93224, 55-17105, 56-4148 55-108667, 55-156953, 56-3 6656, etc.), pyrazoline derivatives and pyrazolone derivatives (US Pat. Nos. 3,180,729 and 4,278, 746, JP-A 55-88064, 55-88065, 49-105537, 55-51086, 56-800 No. 51, No. 56-88141, No. 57-45545, No. 54-112637, No. 55-74546, etc.), Phylenediamine derivatives (US Pat. No. 3,615,404) (See the description, Japanese Patent Publication Nos. 51-10105, 46-3712, 47-25336, JP 54-53435, 54-110536, 54-119925, etc.) Allylamin derivatives (US Pat. No. 3,567,450, 3,180,70) No. 3, No. 3, 240, 597, No. 3, 658, 520, No. 4, 23 2, 103, No. 4, 175, 961, No. 4,012,376, JP-B 49-35702, 39-27577, JP-A 55-144250, 56-119132, 56-22437, West German Patent No. 1,110,518), amino-substituted chalcone derivatives (see US Pat. No. 3,526,501 etc.), oxazole derivatives (US Pat. No. 3,257,203) Etc.), styrylanthracene derivatives (see JP 56-46234 A, etc.), fluorenone derivatives (see JP 54-110837 A, etc.), hydrazone derivatives (US Pat. No. 3,717,462) Specification, JP-A-54-59143, 55-52063, 55-52064, 55-46760, 55-85495, 57-11350, 57- 1487 No. 49 JP-A-2-311591 etc.), stilbene derivatives (JP-A-61-210363, 61-228451, 61-14642, 61-72255, 62- 47646, 62-36674, 62-10652, 62-30255, 60-93455, 60-94462, 60-1747 49, 60- No. 175052, etc.), silazane derivatives (US Pat. No. 4,950,950), polysilanes (JP-A-2-204996), aniline-based copolymers (JP-A-2-282263), Examples of the conductive high-molecular oligomers (particularly thiophene oligomers) disclosed in JP-A-1-211399.

As the material for the hole injection layer or the hole transport layer, the above-mentioned materials can be used. However, Volfirin compound (disclosed in JP-A-63-29556965), aromatic tertiary Amine compounds and styrylamine compounds (US Pat. No. 4,127,412, JP-A 53-27033, 54-58445, 54-149634, 54-6 4299, 55-79450 publication, 55-144250 publication, 56-119132 publication, 61-295558 publication, 61-98353 publication, 63-295695 publication etc.), aromatic tertiary Amine compounds can also be used. Further, for example, 4, 4 ′ bis (N— (1-naphthyl) -N ferro-amino) biphenol having two condensed aromatic rings described in US Pat. No. 5,061,569 in the molecule. In addition, three triphenylamine units described in JP-A-4308688 are connected in a starburst type. , 4, 4, 4, -tris (N- (3-methylphenol) -N-phenolamino) triphenylamine. In addition to the above-mentioned aromatic dimethylidene compounds shown as the material for the light emitting layer, inorganic compounds such as P-type Si and p-type SiC can also be used as the material for the hole injection layer or the hole transport layer.

[0117] As the hole transport material, the aromatic amine derivative represented by the following general formula (1) is desirable.

 [Chemical 26]

[Wherein is a divalent group consisting of a substituted or unsubstituted arylene group having 5 to 60 carbon atoms or a heterocyclic group, and Ar to Ar are each a substituted or unsubstituted group having 5 to 50 nuclear atoms.

 7 10

 It is a substituent or a substituent represented by the following general formula.

 [Chemical 27]

(In the formula, L is a substituted or unsubstituted arylene group or heterocyclic group having 5 to 60 carbon atoms.

 2

 Ar to Ar are substituted or unsubstituted, respectively, having 5 to 50 nuclear atoms.

 11 12

 It is a substituent. )]

 [0118] As L and L, biphenylene, terphelene, phenanthrene or fluorene

 1 2

 Preferred are bi-phenylene and terferene, and more preferred is bi-phenylene.

 [0119] As Ar to Ar, biphenyl group, terfel group, phenanthrene group, fluorene

 7 12

Group, 1-naphthyl group, 2-naphthyl group or phenyl group, preferably biphenyl group, terfel group, 1-naphthyl group or phenyl group. [0120] In the compound represented by the general formula (1), Ar to Ar are preferably the same substituent.

 7 10

 That's right. In this case, Ar to Ar are preferably biphenyl groups or terphenyl groups, and more preferably.

 7 10

 Or a biphenyl group.

 [0121] In addition, the compound represented by the general formula (1) includes Ar to Ar among substituents of Ar to Ar.

 7 10 8 10 are preferably the same substituent. In this case, Ar to Ar are preferably biphenyl groups.

 8 10

 A terfel group, more preferably a biphenyl group, and Ar is preferably a biphenyl group, a terfel group, a phenanthrene group, a fluorene group, a 1-naphthyl group, a 2-naphthyl group, or A phenyl group, more preferably a biphenyl group, a terfel group, a 1-naphthyl group or a phenyl group. More preferably, Ar to Ar are biphenyl, and Ar is

 8 10 7 Turfyl group, 1 naphthyl group.

 [0122] Further, in the compound represented by the general formula (1), at least three of the substituents Ar to Ar are

 7 10

 Different substituents are preferred. Ar to Ar are preferably biphenyl groups, ter

 7 12

 A phenyl group, a phenanthrene group, a fluorenyl group, a 1-naphthyl group, a 2-naphthyl group or a phenyl group, more preferably a biphenyl group, a terfel group, a 1-naphthyl group or a phenyl group. It is. More preferably, Ar to Ar are biphenyl, and Ar is turf.

 9 10 7

 -L group, 1 naphthyl group, Ar is a phenyl group.

 8

 [0123] As the hole injection layer, a compound represented by the following formula can be used.

 [Chemical 28]

(Where R, R, R, R, R, R are substituted or unsubstituted alkyl groups, substituted or unsubstituted

 1 2 3 4 5 6

 A substituted aryl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted heterocyclic group is shown. However, R, R, R, R, R, and R may be the same or different. Also

 1 2 3 4 5 6

 R and R, R and R, R and R, or R and R, R and R, R and R may form a condensed ring.

1 2 3 4 5 6 1 6 2 3 4 5

Good. ) [0124] More preferred are the following compounds:

 [Chemical 29]

[0125] This hole injection layer or hole transport layer may be composed of one or more of the above-described materials, and what is a hole injection layer or hole transport layer? A hole injection layer or a hole transport layer made of another kind of compound may be laminated! / ヽ. The thickness of the hole injection layer or the hole transport layer is not particularly limited, but is preferably 20 to 200 nm.

[0126] The organic semiconductor layer is a layer that assists hole injection or electron injection into the light-emitting layer, and preferably has a conductivity of 10 " ¹⁰ SZcm or more. For example, thiophene-containing oligomers may include conductive oligomers such as allylamin oligomers described in JP-A-8-193191, conductive dendrimers such as allylamamine dendrimers, and the like. The thickness of the layer is not particularly limited, but is preferably 10 to: L, OOOnm.

 [0127] (2) Second organic layer

An electron injection layer, an electron transport layer, or the like can be provided as the second organic layer between the cathode and the second light emitting layer. The electron injection layer or the electron transport layer is a layer that assists the injection of electrons into the light emitting layer and has a high electron mobility. The electron injection layer is provided to adjust the energy level, such as to alleviate sudden changes in energy level. As a material used for the electron injection layer or the electron transport layer, 8-hydroxyquinoline or a metal complex of its derivative, an oxadiazole derivative, or a nitrogen-containing heterocyclic derivative is preferable. Specific examples of the above-mentioned metal complexes of 8-hydroxyquinoline or its derivatives include metal chelate oxinoid compounds containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline), for example, tris (8-quinolinol) aluminum. Can be used. As the oxadiazole derivative, the following formula [Chemical 30]

(In the formula, Ar ⁵⁰ , Ar ⁵¹ , Ar ⁵² , Ar ⁵⁴ , Ar ⁵⁵ and Ar ⁵⁸ each represent an aryl group with or without a substituent, Ar ⁵ ° and Ar ⁵¹ , Ar ⁵² and Ar ⁵⁴ , Ar ⁵⁵ and Ar ⁵⁸ may be the same or different from each other Ar ⁵³ , Ar ⁵⁶ and Ar ⁵⁷ each represent an arylene group having or not having a substituent, and Ar ⁵⁶ and Ar ⁵⁷ are identical to each other. However, they may be different from each other. Examples of aryl groups in these formulas include a phenyl group, a biphenyl group, an anthranyl group, a perylenyl group, and a pyrenyl group. Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, an anthrene group, a perylene group, and a pyrenylene group. Examples of the substituent for these include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cyan group. As this electron transfer composite, those having good thin film formability are preferably used. Specific examples of these electron transfer compounds include the following.

[Chemical 31]

[0128] The nitrogen-containing heterocyclic derivative is a metal complex including the structures shown in the following (a) to (c).

V and nitrogen-containing compounds are mentioned.

[0129] (a) = N—5- or 6-membered ring containing skeleton

[0130] (b)

 [Chemical 32]

(In the formula, X represents a carbon atom or a nitrogen atom. Z and Z each independently contain nitrogen.

 1 2

 Represents a group of atoms capable of forming a prime heterocycle. )

 [0131] (c)

[Chemical 33] N-

(3) In addition, the nitrogen-containing heterocyclic derivative preferably has a nitrogen-containing aromatic polycyclic group such as a 5-membered ring or a 6-membered ring, and if it contains a plurality of nitrogen atoms, it is not adjacent to the! And an organic compound having a skeleton. In the case of such a nitrogen-containing aromatic polycyclic group having a plurality of nitrogen atoms, examples thereof include nitrogen-containing aromatic polycyclic organic compounds having a skeleton combining (a) and (b) or (a) and (c). It is done.

 Further, examples of the nitrogen-containing heterocyclic derivative include the compounds shown in the following (d) to (g).

(d) A nitrogen-containing heterocyclic derivative containing a nitrogen-containing heterocyclic group selected from the following formulae.

[Chemical 34]

(In the formula, R is an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and n is 0 to An integer of 5 Yes, when n is an integer greater than or equal to 2, several R may mutually be same or different. [0133] (e) Further, as a preferred specific compound, a nitrogen-containing heterocyclic derivative represented by the following formula:

HAr-L-Ar ⁶¹ -Ar ⁶²

(In the formula, HAr is a nitrogen-containing heterocycle having 3 to 40 carbon atoms which may have a substituent, and L may have a single bond or a substituent, and may have 6 to 40 carbon atoms. Or a heteroarylene group having 3 to 40 carbon atoms, and Ar ⁶¹ may be a divalent divalent 6 to 40 carbon atom that may have a substituent. Ar ⁶² may have a substituent, Ar ⁶² may have an aryl group or a substituent having 6 to 40 carbon atoms! /, May! /, 3 to 40 carbon atoms The heteroaryl group.)

 [0134] Examples of HAr include the following groups.

[Chemical 35]

[化 37]

[Chemical 37]

[0137] Examples of Ar ^bl include the following groups.

 [Chemical 38]

(Wherein R ^{bl to} R "each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 40 carbon atoms, The aryl group having 6 to 40 carbon atoms or the heteroaryl group having 3 to 40 carbon atoms may have a substituent, and Ar ⁶³ may each have a substituent. It is an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms.)

Preferably, R ^{61 to} R ⁷⁴ are all hydrogen atoms.

[0138] (f) The following compounds described in JP-A-9 3448

 [Chemical 39]

(式中、 R⁸¹〜R⁸⁴は、それぞれ独立に、水素原子、置換もしくは未置換の脂肪族基、 置換もしくは未置換の脂肪族式環基、置換もしくは未置換の炭素環式芳香族環基、 置換もしくは未置換の複素環基を表し、 X⁸¹, X⁸²は、それぞれ独立に、酸素原子、硫 黄原子もしくはジシァノメチレン基を表す。 )

(In the formula, each of R ^{81 to} R ⁸⁴ independently represents a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aliphatic cyclic group, or a substituted or unsubstituted carbocyclic aromatic ring group. And represents a substituted or unsubstituted heterocyclic group, and X ⁸¹ and X ⁸² each independently represents an oxygen atom, a sulfur atom or a dicyanomethylene group.)

[0139] (g) The following compounds described in JP-A-2000-173774

 [Chemical 40]

[Wherein, R ⁹¹ , R 3, R ^9d and R ⁹⁴ are the same or different groups, and are aryl groups represented by the following formulae.

 [Chemical 41]

(In the formula, R ⁹⁵ , R ⁹⁶ , R ⁹⁷ , R ⁹⁸ and R ⁹⁹ are the same or different from each other, and a hydrogen atom or at least one of them is a saturated or unsaturated alkoxyl group, alkyl group, amino A group or an alkylamino group.

[0140] (h) Further, it may be a polymer compound containing the nitrogen-containing heterocyclic group or the nitrogen-containing heterocyclic derivative.

 [0141] The thickness of the electron injection layer or the electron transport layer is not particularly limited, but is preferably 1 to: L00 nm o

[0142] The first light-emitting layer or the first organic layer, which is the organic layer closest to the anode, preferably contains an oxidizing agent. Preferred oxidizing agents are electron withdrawing or electron acceptors. The electron withdrawing or electron acceptor is preferably an electron withdrawing substituent or electron. An organic compound having a deficient ring.

 Examples of the electron-withdrawing substituent include halogen, CN—, carbo group, aryl group and the like.

 As an electron-deficient ring, f-pyridinole, 3-pyridinole, 4-pyridinole, 2-quinolinole, 3-quinolyl, 4-quinolyl, 2-imidazole, 4-imidazole, 3-pyrazole, 4-pyrazole, pyridazine, pyrimidine, pyrazine, cinnoline, phthalazine , Quinazoline, quinoxaline, 3— (1, 2, 4—N) —triazolyl, 5— (1, 2, 4—N) —triazolyl, 5—tetrazolyl, 4— (1—O, 3—N) —Oxazole, 5— (1—O, 3—N) —Oxazole, 4 (1 -S, 3-N) thiazole, 5— (1 -S, 3-N) thiazonole, 2 benzoxazole, 2 benzothiazole, 4— (1, 2, 3-N) -benzotriazole and Benz Imidazole Force that includes the selected compound, etc. It is not necessarily limited to these.

Preferred are Lewis acids, various quinone derivatives, dicyanquinodimethane derivatives, and salts formed with aromatic amines and Lewis acids.

 More preferred are quinoid derivatives, and compounds represented by the following formulas (la) to (li) can be mentioned. More preferred are compounds represented by (la) and (lb).

[Chemical 42]

In the formulas (la) to (: Li), R 1 to R 4 are each hydrogen, halogen, a fluoroalkyl group, a cyano group, an alkoxy group, an alkyl group, or an aryl group. Of these, hydrogen and cyano groups are preferred.

In formula (la) ~ (li), ~ 17 is an electron withdrawing group, each independently, comprising any force structure of the following formula (j) ~ (P). Preferably, the structure is (j), (k), or (1).

 [Chemical 43]

0 NC _V CN _N , CN NC ^ CF ₃ NC ^ COOR ⁴⁹ R ⁵⁰ OOC, NO COOR ⁵¹ NC ^ R ⁵² 0) (k) (1) (m) (n) (o) (p)

(Wherein R ^{49 to} R ⁵² are each a hydrogen atom, a fluoroalkyl group, an alkyl group, an aryl group or a heterocyclic ring, and R ⁵ and R ⁵¹ may form a ring.)

In the formulas (la) to (: Li), yi Y ²⁸ each independently represents —N═ or —CH 2.

[0145]! ^ Fluorine and chlorine are preferred as the shaku ⁴⁸ halogen.

! As the fluoroalkyl group of ^ ¹ to! ^ ^48, a trifluoromethyl group or a pentafluoroethyl group is preferable.

As ^ ~ 1 ⁴⁸ alkoxy group, a methoxy group, an ethoxy group, iso- propoxy group, tert - butoxy group are preferable.

The alkyl group of ˜1 ^ ⁴⁸ is preferably a methyl group, an ethyl group, a propyl group, an iso-propyl group, a tert-butyl group, or a cyclohexyl group.

! ^ As Ariru group ~ length ^48, Hue - group, a naphthyl group are preferred.

Fluoroalkyl group, alkyl group, and aryl group of R ^{49 to} R ⁵² are! ^ ~ Same as shaku ⁴⁸ [0146] the heterocyclic ring R ⁴⁹ ~R ^52, U preferred substituents represented by the following formula '

[Chemical 44]

[0147] When R ^∞ and where R ⁵¹ form a ring, X is preferably a substituent represented by the following formula.

 [Chemical 45]

(In the formula, R ⁵¹ ′ and R ⁵² ′ are a methyl group, an ethyl group, a propyl group, and a tert-butyl group, respectively.)

 [0148] Specific examples of the quinoid derivative include the following compounds.

 [Chem 46]

陰極に最も近い有機層である第 2発光層又は第二の有機層が、還元剤を含有して いることが好ましい。好ましい還元剤は、アルカリ金属、アルカリ土類金属、アルカリ金 属酸化物、アルカリ土類酸化物、希土類酸化物、アルカリ金属ハロゲン化物、アル力 リ土類ハロゲンィ匕物、希土類ハロゲンィ匕物、アルカリ金属と芳香族化合物で形成され る錯体である。特に好ましいアルカリ金属は Cs、 Li、 Na、 Kである。

The second light emitting layer or the second organic layer that is the organic layer closest to the cathode preferably contains a reducing agent. Preferred reducing agents are alkali metals, alkaline earth metals, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, alkali metals. And a complex formed of an aromatic compound. Particularly preferred alkali metals are Cs, Li, Na and K.

[0149] In the present invention, the hole transport layer (hole injection layer) is preferably formed using the same material as the charge barrier layer described above. This makes it possible to reduce the types of materials used for manufacturing organic EL elements, which is advantageous in terms of cost in industrial production.

 [Example]

 [0150] The compounds used in Examples and Comparative Examples are shown below.

[Chemical 47] //-0v: 0zfcl> d 099068Π OAV

/ v: /-00ifcl £

RH

 Table 1 shows the energy gap (Eg), ionization potential (Ip), and affinity level (Af) of the above compounds.

[Table 1] Compound IP (eV) Eg (eV) Af (eV)

 BH 5.8 3.0 2.8

 BD 5.5 2.8 2.7

 GD 5.6 2.5 3.1

 RH 5.6 2.4 3.2

 RD 5.5 2.1 3.4

 ET 5.71 2.98 2.73

 HT 5.36 3.06 2.3

 HI 5.3 3.3 2.0

CBP 5.86 3.45 2.41 [0152] The method for measuring the characteristics of the compound is as follows.

 (1) Energy Legacy Gap (Eg)

 Using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu, UV-3100PC), measure the ultraviolet-visible light absorption spectrum of the material solution (solvent: toluene), and calculate an optical band cap that calculates the tangential force on the long wavelength side. The energy gap (Eg) was used.

[0153] (2) Ionization potential (Ip)

 Measurement was performed using an atmospheric photoelectron spectrometer (AC-1 manufactured by Riken Keiki Co., Ltd.). The photoelectrons emitted were plotted against the energy of ultraviolet rays irradiated to the material (powder) in the power of 1Z2, and the threshold of the photoelectron emission energy was defined as the ion potential (Ip).

[0154] (3) Party level (Af)

 Af = IP—Eg.

[0155] (4) Driving voltage

Voltage when the current density is energized between the ITO and A1 so that lOmAZcm ² (Unit: V) was measured.

[0156] (5) Luminous efficiency

The EL spectrum when a current density of 1 OmAZcm ^{2 was} applied was measured with a spectral radiance meter CS 1 OOOA (manufactured by Koryo Minolta) to calculate the luminous efficiency (unit: cd / A).

[0157] (6) CIE1931 chromaticity

The EL spectrum when current density lOmAZcm ^{2 was} applied was measured for CIE1931 chromaticity (x, y) with a spectral radiance meter CS 1000A (manufactured by Koyu Minolta).

[0158] (7) External quantum yield

The EL spectrum when current density 1 OmAZcm ^{2 was} applied was measured with a spectral radiance meter CS 1 OOOA (manufactured by Corminor Minolta) and calculated by the following formula.

 [Number 1]

_{Integrate E0E (0 /)} (spectral radiant intensity ÷ photon energy) with the photon wavelength and then with the solid angle.,-Current density _÷ elementary electron charge

[0159] Example 1 (Formation of organic EL elements)

 25mm X 75mm X 1. 1mm thick glass substrate with ITO transparent electrode (anode) (Zomatic Co., Ltd.) (saddle film thickness 130nm) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, followed by UV ozone cleaning For 30 minutes. The glass substrate with the transparent electrode line after washing is mounted on the substrate holder of the vacuum evaporation system, and first, an HI film with a film thickness of 60 nm is formed on the surface where the transparent electrode line is formed so as to cover the transparent electrode. Filmed. This HI film functions as a hole injection layer. Following the formation of the HI film, a HT film with a thickness of 15 nm was formed on the HI film. This HT film functions as a hole transport layer.

[0160] Furthermore, following the formation of the HT film, RH (Eg: 2.4 eV) and RD were set at a film thickness of 5 nm.

 The first light emitting layer (IpZAf (eV) = 5.6 / 3.2) was formed by vapor deposition and film formation so as to be 5% by weight. The first light emitting layer emits red light. Next, an HT film (I p / Af [eV] = 5.36 / 2.3) having a thickness of 5 nm was formed as a charge barrier layer. BH and BD are vapor-deposited on the charge barrier layer so that BD is 7.5% by weight, and a blue light-emitting layer (second light-emitting layer) with a thickness of 40 nm (lp / Af [e V] = 5. 8/2. 8). On this film, a 20 nm-thick tris (8-quinolinol) aluminum film (Alq film) was formed as an electron transport layer. After this, a LiF film as an electron injection layer 1.

 Three

 6 nm was formed. On this LiF film, metal A1 was deposited by 150 nm to form a metal cathode to form an organic EL light emitting device.

[0161] (Evaluation of organic EL devices)

 FIG. 5 shows the energy levels of the first light-emitting layer, the first charge barrier layer, and the second light-emitting layer prepared in Example 1. The characteristics of the obtained organic EL light emitting device were measured. The results are shown in Table 2.

[0162] Comparative Example 1

 In Example 1, an organic EL light emitting device was formed in the same manner as in Example 1 except that the first light emitting layer was formed and then the charge barrier layer was not formed. The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 2 shows the measurement results.

[0163] Comparative Example 2

In Comparative Example 1, the thickness of the hole transport layer was set to 10 nm, the thickness of the first light emitting layer was set to 40 nm, the thickness of the electron transport layer was set to 30 nm, and the film formation of the second light emitting layer was omitted. Same as example 1 Thus, an organic EL light emitting device was formed. The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 2 shows the measurement results.

[0164] Comparative Example 3

 In Comparative Example 1, the thickness of the hole transport layer was 20 nm, the thickness of the second light emitting layer was 40 nm, and the film formation of the first light emitting layer was omitted. Formed. The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 2 shows the measurement results.

[0165] Comparative Example 4

 In Example 1, an ET film (IpZAf [eV] = 5. 71/2. 73) was formed as a charge barrier layer in place of HT with a thickness of 5 nm. A light emitting device was formed. FIG. 6 shows the energy levels of the first light-emitting layer, the first charge barrier layer, and the second light-emitting layer prepared in Comparative Example 4. The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 2 shows the measurement results.

[0166] Example 2

 In Example 1, after forming the second light-emitting layer with a film thickness lOnm, as the third light-emitting layer, BH and GD were vapor-deposited at a film thickness of 30 nm so that GD would be 10% by weight. IpZAf [eV] = 5.8 / 2.8) and after forming a green light emitting layer, an Alq layer (electron transport layer) was formed.

 Three

 In the same manner as in 1, an organic EL light emitting device was formed. The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 2 shows the measurement results.

[0167] Comparative Example 5

 In Example 2, a CBP film (IpZ Af [eV] = 5.86 / 2.41) was formed as a charge barrier layer in place of HT with a thickness of 5 nm. An EL light emitting device was formed. FIG. 7 shows the energy levels of the first light-emitting layer, the first charge barrier layer, and the second light-emitting layer prepared in Comparative Example 5. The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 2 shows the measurement results.

[0168] Example 3

In Example 1, instead of HT, HT and GD were deposited and deposited (IpZAf [eV] = 5. 36/2. 3) so that GD would be 10 wt% instead of HT. The thickness of the two light emitting layers is 4 An organic EL light emitting device was formed in the same manner as in Example 1 except that Onm was used. The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 2 shows the measurement results.

[0169] Example 4

In Example 2, instead of HT as a charge barrier layer, HT and GD were vapor-deposited so that GD would be 5% by weight (I _P ZAf [eV] = 5. 36/2. 3). An organic EL light emitting device was formed in the same manner as in Example 2 except that the thickness of the second light emitting layer and the third light emitting layer was 15 nm and 25 nm, respectively.

 The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 2 shows the measurement results.

[0170] [Table 2]

[0171] In Example 1, the red light emission of Comparative Example 2 and the blue light emission of Comparative Example 3 were combined. By providing a red light-emitting layer with a small energy gap as the first light-emitting layer on the anode side and a blue light-emitting layer with a large energy gap as the second light-emitting layer, and providing a charge barrier layer with a small affinity level between them, each single color As a result, it was possible to obtain white light emission that was higher than that of the external quantum yield in Fig. 5 (Fig. 5).

 In Example 2, by adding a green light-emitting layer as the third light-emitting layer to Example 1, it was possible to obtain good white light emission with higher current efficiency and an equivalent external quantum yield.

 In Example 3, by further doping the charge barrier layer with a green light emitting material as compared with Example 1, it was possible to obtain good white light emission with an equivalent external quantum yield.

 [0172] In Comparative Example 4, since an electron-transporting charge barrier layer having a high affinity level was provided, redness was further increased and efficiency was lowered (Fig. 6).

 In Comparative Example 5, the ionization potential is large and the facet is small, and since the charge barrier layer is provided, the holes remain in the first light emitting layer, and the redness increases compared to Example 2, resulting in good white light emission. I couldn't get it (Fig. 7).

[0173] In Comparative Example 1, CIE1931 chromaticity (x, y) is close to white (0.33, 0.33) in the range of luminance 10 to: LOOOOcdZm ² , and the power is greatly separated, redness is increased and good white It was not good. In Examples 1 to 4, the chromaticity (X, y) is near white, and good white light emission can be obtained. In particular, Example 3 was able to obtain better white light emission with a change in chromaticity (x, y) in the range of luminance 10 to: LOOOOcdZm ² with less change than Examples 1-2 and Example 4 (Fig. 8, Figure 9).

 [0174] Comparative Example 6

 An organic EL device was produced in the same manner as in Example 1 except that the compositions of the first light emitting layer, the electron blocking layer, and the second light emitting layer were changed as shown in Table 3. That is, the cathode side of the charge barrier layer is a red light emitting layer. An amine hole transport material (GD) with an Af of about 3. leV was used as the charge barrier layer. The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 3 shows the measurement results.

(CIEx, CIEy) = (0. 657, 0. 340) and only the red of the second light emitting layer was shining. Also light emitting The efficiency was also poor.

[0175] Comparative Example 7

 An organic EL device was produced in the same manner as in Example 1 except that the compositions of the first light emitting layer and the second light emitting layer were changed as shown in Table 3. That is, as in Comparative Example 6, the cathode side of the charge barrier layer is a red light emitting layer. Here, the Af of the host of the first light emitting layer is made higher than the Af of the charge barrier layer. The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 3 shows the measurement results.

 (CIEx, CIEy) = (0. 657, 0. 340) and only the red light in the second light emitting layer was lit, and the efficiency was poor. In this case as well, the light emission is only red, and electrons are not injected into the first light emitting layer (blue), and the white color is not good.

 Thus, from the above two comparative examples, when the Eg of the host of the second light emitting layer is smaller than the Eg of the host of the first light emitting layer, the light emission balance cannot be achieved no matter how the Af level of the charge barrier layer is devised. I understand that.

 Therefore, it is necessary that Eg of the second light emitting layer is larger than Eg of the first light emitting layer.

[0176] Comparative Example 8

 An organic EL device was produced in the same manner as in Example 1 except that the compositions of the first light emitting layer, the electron blocking layer, and the second light emitting layer were changed as shown in Table 3. That is, the first light emitting layer was green and the second light emitting layer was blue. The charge barrier layer was doped with red (RD). The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 3 shows the measurement results.

 From the chromaticity data, the energy recombined at the interface between the charge barrier layer Z and the second light-emitting layer moves to the blue dopant and the red dopant and emits light. I found out that I was helped.

[0177] Comparative Example 9

 An organic EL device was produced in the same manner as in Example 1 except that the compositions of the first light emitting layer, the electron blocking layer, and the second light emitting layer were changed as shown in Table 3. That is, the first light emitting layer was blue, the second light emitting layer was red, and the charge barrier layer was doped with green. The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 3 shows the measurement results.

As shown in the chromaticity data, the luminescence was almost red. [0178] As shown in Example 3 and Comparative Examples 8 and 9, in order to form a well-balanced three-wavelength white color, it is preferable to arrange blue, which emits less light, in the region where it is most recombined. Therefore, blue becomes the second light emitting layer. From the balance of the host material, red is placed in the first light emitting layer. This configuration provides a well-balanced white color.

 Furthermore, when the charge barrier layer is doped with green, green can be emitted by exciton energy generated in the interface region between the charge barrier layer and the second light emitting layer. Further, since the charge barrier layer constituting the recombination region is doped with green at the interface with the first and second light emitting layers, the green light emission is stabilized. Green, which is highly visible, can be easily seen by human eyes when the light emission balance is lost. Therefore, by arranging green at the position where the balance is most balanced, it is possible to make white with little color shift.

 [0179] Example 5

 An organic EL device was manufactured in the same manner as in Example 2 except that the compositions of the second light emitting layer and the third light emitting layer were changed as shown in Table 3. The obtained organic EL light emitting device was measured in the same manner as in Example 1. Table 3 shows the measurement results.

 As shown in the chromaticity data, the blue light emission near 460 nm was weak, and a suitable white light emission was not obtained. This is because the blue light emission is weakened because it is difficult to transfer energy to the blue light-emitting layer due to recombination near the charge barrier layer Z second light-emitting layer (green) interface and green light emission.

 [0180] As can be seen from the comparison between Example 2 and Example 5, in Example 2, the recombination energy in the second light-emitting layer is transferred to the third light-emitting layer to emit green light in the third light-emitting layer. . In the second embodiment, since green is arranged on the cathode side with respect to blue, a non-lance of electron injection with respect to blue can be obtained. This is because the green dopant becomes an electron trap. As a result, a balanced white element configuration can be realized as a whole.

[0181] [Table 3]

[0182] Example 6

 (Full color light emitting device)

 112mmX 143mm X I. On a 1mm support substrate (OA2 glass: manufactured by Nippon Electric Glass Co., Ltd.) V259BK (manufactured by Nippon Steel Chemical Co., Ltd.) is spin coated as a material for Black Mato Tutus (BM), opening 68 m X 285 m After exposure to ultraviolet rays through a photomask that creates a grid pattern, develop with 2% aqueous sodium carbonate, and beta at 200 ° C to form a black matrix (thickness 1.5 m) pattern. Formed.

 [0183] Next, as a blue color filter material, V259B (manufactured by Nippon Steel Chemical Co., Ltd.) was spin-coated to obtain 320 rectangular stripe patterns (100 μm line, 230 μm gap). , Aligned with BM, exposed to UV light, developed with 2% aqueous sodium carbonate solution, beta-treated at 200 ° C to form a blue color filter (thickness 1.5 m) pattern .

 [0184] Next, as a green color filter material, V259G (manufactured by Nippon Steel Chemical Co., Ltd.) was spin-coated to obtain 320 rectangular stripe patterns (100 μm line, 230 μm gap). , Align with BM, expose to ultraviolet light, develop with 2% aqueous sodium carbonate solution, beta at 200 ° C, and place a green color filter (film thickness 1.5%) adjacent to the blue color filter. The pattern of m) was formed.

 [0185] Next, as a material for the red color filter, CRY-S840B (manufactured by Fuji Film Arch) was spin-coated to obtain 320 rectangular patterns (100 μm line, 230 μm gap). Aligned with BM through a photomask, exposed to UV light, developed with 2% aqueous sodium carbonate, betaed at 200 ° C, and red color filter (between the blue color filter and green color filter ( A pattern with a film thickness of 1.5 m) was formed.

 [0186] Next, an acrylic thermosetting resin (V259PH: manufactured by Nippon Steel Chemical Co., Ltd.) was spin-coated on the previous substrate as a flattening film, and beta-coated at 180 ° C. 5 m) was formed. Next, ITO (indium stannate) was deposited by sputtering to a thickness of 130 nm.

[0187] Next, a positive resist (HPR204: manufactured by Fuji Orin) is spin-coated on this substrate, and a cathode taking out part and a photomask that forms a striped pattern of 90 m line and 20 m gap are formed. Through UV exposure and development of tetramethylammonium hydroxide The resist was developed with a solution and beta-treated at 130 ° C.

 [0188] Next, the exposed ITO was etched with an ITO etchant. Next, the resist was treated with a stripping solution mainly composed of ethanolamine (N303: manufactured by Nagase Sangyo), and ITO pattern (lower electrode) was placed on the blue color filter, green color filter, and red color filter. : Anode, number of lines 960).

 [0189] Next, as the first interlayer insulating film, a negative resist (V259PA: manufactured by Nippon Steel Chemical Co., Ltd.) is spin-coated, exposed to ultraviolet rays through a photomask, and then developed with a developer of tetramethylammonium hydroxide. Developed. Next, beta was formed at 180 ° C., and an ITO opening covering the ITO edge was 70 m × 290 m) to form a lattice-patterned interlayer insulating film.

 [0190] Next, as a second interlayer insulating film (partition), a negative resist (ZPN1100: manufactured by Nippon Zeon Co., Ltd.) was spin-coated and passed through a photomask that formed a stripe pattern with 20 m lines and 310 m gaps. After UV exposure, beta after exposure was further performed. Next, the negative resist was developed with a developer of tetramethylammonium hydroxide to form a second interlayer insulating film (partition) perpendicular to the ITO stripe.

 The substrate thus obtained was subjected to ultrasonic cleaning in pure water and isopropyl alcohol, dried by air blow, and then UV cleaned.

 [0191] Thereafter, the organic layer (from the hole injection layer to the electron injection layer) was mask-deposited in a range covering the color filter, and the cathode was further subjected to mask deposition so that it could be connected to the previously formed ITO extraction electrode. . The cathode (upper electrode) was automatically separated by the partition walls previously formed on the substrate, and had a pattern (240 lines) intersecting the lower electrode.

 [0192] After manufacturing the organic EL element on the substrate, move the substrate to the dry box where dry nitrogen was circulated so as not to be exposed to the atmosphere, and cover the display part with the blue plate glass of the sealing substrate in the dry box. The peripheral part of the display part was sealed by photocuring with a cationic curable adhesive (TB3102: manufactured by ThreeBond).

 [0193] In this way, a full-color light emitting device in which the lower electrode and the upper electrode form an XY matrix is manufactured, and a DC voltage is applied to the lower electrode and the upper electrode (lower electrode: (+), upper electrode) : (1)) As a result, the intersection (pixel) of each electrode emitted light.

[0194] (Characteristic evaluation of full-color light-emitting device) (1) Blue performance

When a DC voltage of 7.25 V was applied between the lower electrode corresponding to the blue color filter and the upper transparent electrode, it emitted blue light. When measured with a spectral radiance meter CS-1000 (manufactured by Minolta), the luminance was 31 cdZm ² and the chromaticity (0.124, 0.117). When the current flowing between the two electrodes was measured and the luminous efficiency was calculated, it was 1.14 cdZA.

[0195] (2) Green performance

When a DC voltage of 7.25 V was applied between the lower electrode corresponding to the green color filter and the upper transparent electrode, it emitted green light. When measured with a spectral radiance meter CS-1000 (manufactured by Minolta), the luminance was 250 cdZm ² and the chromaticity (0.247, 0.621). The value of the current flowing between the two electrodes was measured and the luminous efficiency was calculated to be 9.24 cdZA.

[0196] (3) Red performance

When a DC voltage of 7.25 V was applied between the lower electrode corresponding to the red color filter and the upper transparent electrode, it emitted red light. When measured with a spectral radiance meter CS-1000 (manufactured by Minolta), the luminance was 85 cdZm ² and the chromaticity (0.652, 0.335). The current flowing between the two electrodes was measured and the luminous efficiency was calculated to be 3.15 cdZA.

[0197] (4) Fully lit

When a DC voltage of 7.25 V was applied between all the lower electrodes and the upper transparent electrode, white light was emitted. When measured with a spectral radiance meter CS-1000 (manufactured by Minolta), the luminance was 451 cdZm ² and the chromaticity (0.324, 0.397). When the current flowing between the two electrodes was measured and the luminous efficiency was calculated, it was 4.51 cdZA, which was very high.

 Industrial applicability

[0198] The organic EL device of the present invention can be used for various display devices, knocklights, full-color display devices using color filters, light sources for general illumination and special illumination.

Claims

 The scope of the claims  [1] An anode, a first light emitting layer, a charge barrier layer, a second light emitting layer and a cathode are laminated in this order, and the first light emitting layer and the second light emitting layer each contain a host material and a dopant, The energy gap force of the host material of the first light emitting layer is smaller than the energy gap of the host material of the second light emitting layer,  The host material of the first light emitting layer is a hole transporting material, the host material of the second light emitting layer is an electron transporting material,  The affinity level force of the charge barrier layer is 0.2 eV or more smaller than the affinity level of the host material of the second light emitting layer,  Ion potential (Iel) of the charge barrier layer and ion potential (Ihl) 1S of the host material of the first light emitting layer 1S An organic electoluminescence device that satisfies the following relationship (1).  IeKIhl + O. 1 (eV) · · · (1) [2] including an anode, a first light emitting layer, a charge barrier layer, a second light emitting layer, a third light emitting layer, and a cathode laminated in this order,  The first light-emitting layer, the second light-emitting layer, and the third light-emitting layer contain a host material and a dopant, respectively;  The energy gap force of the host material of the first light emitting layer is smaller than the energy gap of the host material of the second light emitting layer,  The host material of the first light emitting layer is a hole transporting material;  The host material of the second light emitting layer and the third light emitting layer is an electron transporting material, and the charge barrier layer is a hole transporting material,  Ion potential (Iel) of the charge barrier layer and ion potential (Ihl) 1S of the host material of the first light emitting layer 1S An organic electoluminescence device that satisfies the following relationship (1).  IeKIhl + O. 1 (eV) · · · (1) [3] The organic electroluminescent device according to claim 2, wherein the affinity level force of the charge barrier layer is 0.2 eV or more smaller than the affinity level of the host material of the second light emitting layer. [4] The energy gap force of the host material of the first light-emitting layer is 0.4 eV or less smaller than the energy gap of the host material of the second light-emitting layer! /, Claims 1-3! Organic-elect mouth luminescence element.  5. The organic electroluminescent device according to claim 1, wherein the dopant of the first light emitting layer is a red dopant, and the dopant of the second light emitting layer is a blue dopant. [6] The dopant of the first light emitting layer is a red dopant, the dopant of the second light emitting layer is a blue dopant, and the dopant of the third light emitting layer is a green dopant. The organic electoluminescence device according to 2 or 3. 7. The organic electroluminescent element according to any one of claims 1 to 6, wherein the charge barrier layer contains a light emitting material.  8. The organic electroluminescent device according to claim 7, wherein the light emitting material of the charge barrier layer is a green dopant.  9. The organic electoluminescence device according to any one of claims 1 to 8, further comprising a hole transport layer adjacent to the first light emitting layer between the anode and the first light emitting layer.  10. The organic electroluminescent device according to claim 9, wherein the material forming the hole transport layer and the material forming the charge barrier layer are the same material.  [11] The second light-emitting layer or the second organic layer in which the first light-emitting layer or the first organic layer that is an organic layer close to the anode is an organic layer close to the force containing Z and the cathode or the oxidant. The organic electoluminescence device according to any one of claims 1 to 10, comprising a force reducing agent.  [12] The host material of the first light emitting layer is a compound represented by the following formula (1), and the dopant of the first light emitting layer is a compound having a fluoranthene skeleton or a perylene skeleton. ~: The organic electoluminescence device according to any one of L1.  X-(Y) n (1)  (In the formula, X is a condensed aromatic ring group having 3 or more carbon rings, Υ is a substituted or unsubstituted aryl group, a substituted or unsubstituted dialyl amino group, a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group A group to be selected,  n is an integer of 1 to 6, and when n is 2 or more, Y may be the same or different. The compound having the fluoranthene skeleton or perylene skeleton is represented by the following formula (2) or formula (2) 13. The organic electroluminescence device according to claim 12, which is an indenoperylene derivative represented by 3).  [Chemical 48]

(Where

Ar ² and Ar ³ are each a substituted or unsubstituted aromatic ring group or a substituted if Ku unsubstituted aromatic heterocyclic group, ^1-8 each represent hydrogen, halogen, alkyl group, alkoxy group, alkylthio group , Alkenyl group, alkoxy group, alkenyl group, aromatic ring-containing alkyl group, aromatic ring-containing alkyloxy group, aromatic ring-containing alkylthio group, aromatic ring group, aromatic heterocyclic group, aromatic ring oxy group, Aromatic ring thio group, aromatic ring alkenyl group, alkenyl aromatic ring group, amino group, carbazolyl group, cyano group, hydroxyl group, -COOR ¹ ′ (R ¹ ′ is hydrogen, alkyl group, alkenyl group, aromatic ring-containing alkyl group Or COR ² ′ (R ² ′ is hydrogen, alkyl group, alkenyl group, aromatic ring-containing alkyl group, aromatic ring group or amino group), or OCOR ³ ′ (R ³ ′ is Alkyl group, alkenyl group It is an aromatic ring is containing alkyl group or aromatic ring group). Adjacent groups of to ^18, but it may also form a ring together with the carbon atom bonded to, or substituted for each other. )  14. The organic electoluminescence device according to claim 13, wherein the indenoperylene derivative is a dibenzotetraphenyl perifuranthene derivative. [15] The host material of the first light emitting layer has 4 or more condensed rings, and the host material of the second light emitting layer has 3 or less condensed rings. Organic electrification luminescence element. The compound power represented by said Formula (1) The organic electoluminescence device of Claim 12-15 which is a naphthacene derivative represented by following formula (4).  [Chemical 49]

 ( Four ) (In formula (4), (^ to ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 nuclear carbon atoms, amino Group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 20 nuclear carbon atoms, substituted or unsubstituted 6-20 aralkylthio group, substituted or unsubstituted alkenyl group having 2-20 carbon atoms, substituted or unsubstituted aralkyl group having 7-20 carbon atoms, or substituted or unsubstituted nuclear atoms 5-20 And these may be the same or different.) 17. The organic electroluminescent device according to claim 16, wherein at least one of QQ ² , Q ³ and Q ^{4 in} the naphthacene derivative represented by the formula (4) is an aryl group.  18. The organic electoluminescence device according to claim 17, wherein the naphthacene derivative represented by the formula (4) is represented by the following formula (5). [Chemical 50]

(In the formula (5), Q ^{3 to} Q ¹² , Q ¹⁰¹ to Q ¹⁰⁵ , Q ^{201 to} Q ² ° ⁵ each independently represents the same group as Q ^{3 to} Q ¹² in the general formula (1), These two, which may be the same or different, may be bonded to each other to form a ring. [19] In the naphthacene derivative represented by the formula (5), at least one of Q ^lcn , Q ¹⁰⁵ , Q ^2Cn and Q ² ° ⁵ is an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group. 19. The organic electroluminescent device according to claim 18, which is an alkylthio group, an arylthio group, an alkenyl group, an aralkyl group or a heterocyclic group, which may be the same or different.  [20] The organic elect according to any one of claims 12 to 19, wherein the charge barrier layer includes a tertiary amine compound, a force rubazole derivative, a compound containing a nitrogen-containing heterocyclic ring, or a metal complex. Mouth luminescence element.  [21] The organic electoluminescence device according to any one of claims 1 to 20, which emits white light;  A full-color light emitting device including a color filter.